Method for preparing modified resins and their applications

ABSTRACT

There are herein disclosed a method for preparing a modified resin which comprises thermal/reaction by the use of a norbornenyl group-containing compound typified by norbornenecarboguanamine or its derivative, a method for preparing an epoxy-modified resin which comprises the step of reacting the above-mentioned modified resin and an epoxide, a flame-retarding method, a thermal stabilization method, a compatibilizing method and a surface modification method which comprise utilizing the modified resin, as well as a coating resin composition and an adhesive resin composition containing the modified resin. 
     According to the preparation methods of the present invention, the deterioration of a material scarcely occurs, and a functional group which is excellent in flame retardancy, thermal stability, compatibility and the like can be introduced to the resins. By the utilization of these techniques, there can be obtained a flame-retardant material having a good char formability, a thermally stable material whose molded articles can inhibit heat deterioration, a material excellent in miscibility between different kinds of resins, a surface-modified material which is excellent in adhesion and coating properties and the like.

This application is a divisional of application Ser. No. 08/514,730,filed Aug. 14, 1995, now U.S. Pat. No. 5,674,947.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to the modification of resins such asusual resins, rubbers, waxes and oils. More specifically, it relates tomethods useful to modify such resins, thereby improving properties suchas flame retardancy, thermal stability, compatibility, surfaceproperties such as adhesive properties, coating properties anddyeability as well as electrical properties of the resins, and it alsorelates to the applications of the modified resins.

2. Description of the Related Art

In general, resins are excellent in electrical properties, mechanicalproperties and workability, and so they have widely been used in manyindustrial fields as construction materials, electrical materials,vehicle, e.g., automotive materials, fiber materials, equipmentmaterials and utensil materials.

However, these resins are extremely easily flammable, and keeping stepwith their extensive use, they have often become a predominant firecause and a fuel source in the fire. Thus, the safety of the resins asthe industrial materials has been strongly demanded. In addition, theseresins are accompanied by some drawbacks. For example, the performanceof flame retardancy, heat resistance and the like is poor; thermalstability is so practically insufficient as to easily deteriorate byheat, light and the like; and surface properties such as wettability,adhesive properties, coating properties and dyeability are poor, so thatthe applications of these resins are noticeably limited.

Furthermore, with the diversification of the applications of the resins,very high performances and characteristics have been required. However,in order to develop novel kinds of resins and to solve the respectiveproblems in reply to this requirement, some technical and economicalhurdles must be cleared. It has now been desired to improve and impartthe performances of the resins without impairing their originalcharacteristics, and so the development of new materials by themodification and combination of the resins is the extremely importanttheme in the industrial field.

A. Heretofore, as methods for improving and imparting thecharacteristics of a resin, there are known, for example, a method forproviding a new kind of resin by the use of a new raw material, a novelsynthesis technique, a novel polymerization technique and the like, anda method for modifying the resin with an already developed resin toimprove and impart the various performances.

In the former method, it is practically difficult or technically veryhard to create the new kind of resin which can meet the above-mentionedrequirements, and another economical problem is also present.

On the other hand, the latter method has conveniences that the resin iseasily available and the characteristics of the resin are alreadygrasped, and the modification method, which comprises, for example, theintroduction reaction of a functional group to the resin, is excellentin economical and technical points, and many suggestions regarding suchmodification methods have been made.

As one of the known modification methods, there is known a techniquewhich comprises carrying out a modification reaction by the use of areactant having the functional group, but for example, such a functionalgroup is bonded only to a terminal position having a specific structureof the resin, or the amount of the functional group is noticeablylimited. For these reasons, the accomplishment of the sufficientmodification is difficult, and the modification or denaturation of theresin by the-use of such a functional group is also hard. In a certaincase, these modification methods are scarcely useful.

Furthermore, there is also known another modification method whichcomprises introducing the functional group to a resin such as apolyolefin resin having no functional group by the use of a reactantsuch as maleic anhydride or acrylic acid and a peroxide such as benzoylperoxide together, and then carrying out a denaturation reaction usingthis functional group to modify the resin. This modification method hasadvantages that the functional group such as a carboxylic acid(anhydride) group which can easily be used for the modification or thesecondary denaturation of the modification can be introduced and apreparation process is relatively easy, but this method issimultaneously accompanied by some disadvantages. For example, since theemployment of the peroxide is required, the decomposition of the resinand the like occurs to noticeably lower the molecular weight. of theresin and to bring about the coloring and quality change of the resin;it is difficult to introduce a large amount of the functional group, sothat the modification of the resin is insufficient; thermal stability,heat resistance and the like deteriorate, and the functional group isseparated off to noticeably accelerate the decomposition of the resin;and the polymerization and the like of the used reactant itself occursto easily form reaction products, so that the physical properties of theresin easily deteriorate inconveniently.

Moreover, in this modification method, it is very difficult to introducethe functional group which is effective for the modification,performance impartment and the like, and thus a manner of adding amodifier having such a functional group can also be used. However, theemployment of such a modifier inconveniently gives rise to thedeterioration of the physical properties and characteristics of theresin.

The above-mentioned known modification methods are still impractical,and they are noticeably limited for technical and economical reasons.

The present inventors have intensively investigated with the intentionof overcoming the above-mentioned drawbacks of the modification methodsfor resins, and as a result, it has been found that by reacting a resinwith a compound quite different from compounds used in the known methodsin structure and characteristics under specific reaction conditions, theresin can be successfully modified. According to this modificationmethod, even if a large amount of the functional group is introduced tothe resin, the molecular weight, physical properties and quality of themodified resin scarcely deteriorate; the amount of the functional groupto be introduced can be selected in a wide range, and so themodification and performance impartment can easily be controlled; theuse of a peroxide is not required, and hence the conditions of amodification reaction are moderate, a process is easy to conduct, andside reactions can be inhibited to prevent the decomposition and thusthe quality change of the resin; since the functional group having anexcellent modification and performance impartment power can beintroduced and bonded to the resin without adding and mixing thecompound having such a functional group, the physical properties of theresin are not impaired; even for the resin not having a functional groupsuch as a carboxylic acid group, an amino group or a double bond group,the modification and performance impartment can be accomplished by theintroduction of the functional group; the functional group whichscarcely brings about the deterioration by heat or the like and which iscapable of remarkably improving heat resistance can be introduced andbonded to the resin; and the functional group for improving propertiessuch as flame retardancy, compatibility, surface properties such aswettability, adhesive properties, coating properties and dyeability,electrical properties, moldability and the like can be introduced andbonded to the resin to accomplish the modification and performanceimpartment. In consequence, a method for preparing the modified resinhaving the above-mentioned features can be provided.

In addition, it has also be found that when the modified resin obtainedby the above-mentioned method is reacted with an epoxide under specificreaction conditions, an epoxy-modified resin can be obtained which ismore excellent in surface properties such as wettability, coatingproperties, adhesive properties, dyeability and chemical resistance,electrical properties, moldability, compatibility and dispersibilitywith an other resin in addition to above-mentioned good features andwhich can be widely used for various modifications. In consequence, amethod for preparing the epoxy-modified resin can be provided. On thebasis of the findings of these preparation methods, the presentinvention has now been attained.

B. For the purpose of improving the flame retardancy of a resin, variousmethods have been suggested. For example, there have been suggested amethod which comprises adding a flame-retardant to the resin, and amethod which comprises using a flame retardancy-imparting material(inclusive of a halogen monomer) at the manufacture of the resin toincorporate the flame retardancy into the skeleton of the resin.

Among these techniques, the former method which comprises adding theflame-retardant to the resin has usually often been used, and examplesof the known flame-retardant include halogen-containing compounds,phosphorus-containing compounds, inorganic compounds,nitrogen-containing compounds and the like.

When the halogen-containing compound is used as the knownflame-retardant, the modified resin has some drawbacks. For example,heat resistance is usually poor; sublimation and bleeding tend to occur;an effect cannot be obtained in most cases, unless antimony trioxide isused together; and a large amount of an extremely toxichalogen-containing gas is generated in a fire. When thephosphorus-containing compound is used as the flame-retardant, theeffect is insufficient if the compound is used singly, and thehalogen-containing compound is often used together, so that the modifiedresins have the above-mentioned drawbacks. When the inorganic compoundis used, the modified resin has some disadvantages. For example, aninorganic compound such as antimony trioxide is a rare substance ofresources, and hence it is not easily available and there is also theproblem of cost; in the case of aluminum hydroxide, the effect is weakand so it is necessary to add the same in large quantities; the specificgravity of the modified resin increases, the physical properties andmoldability of the resin tend to deteriorate and the heat resistance ofthe resin deteriorates owing to contained water component. In addition,when the nitrogen-containing compound. typified by triazinenucleus-containing compound is used, the modified resin has-thefollowing disadvantages. For example, sublimation, bleeding and the liketend to occur at molding; the manufacturing of the raw material isdifficult, and the material cost is high; the physical properties andcharacteristics of the resin are liable to deteriorate owing to theadded additive; the additive is lost with time, and the dispersabilityand miscibility of the additive also lowers, so that a flame-retardanteffect noticeably decreases; and since a large amount of the additive isrequired to be added, the characteristics and physical properties of theresin are outstandingly impaired.

As the latter method, there is known a technique in which a materialcontaining bromine, phosphorus or the like is incorporated as the flameretardancy-imparting material into the resin at the time ofmanufacturing. In this case, the loss, insufficient dispersion and thelike of an effective flame-retardant component can be prevented, so thatthe reduction of the effect can be minimized, with the result that thephysical properties, characteristics and the like of the resin can beeasily advantageously maintained. However, this method has someinconveniences. For example, it is difficult to manufacture the flameretardancy-imparting material; a material cost is high; the acquisitionof the flame retardancy-imparting material suitable for the manufactureof the resin is noticeably limited and can technically scarcely beobtained; it is very difficult or quite impossible to introduce and bondthe flame retardancy-imparting material to the resin owing to therestriction on the manufacture of the resin, so that the desired resincan scarcely be provided; since the thermal stability of the flameretardancy-imparting material is poor, the thermal stability, heatresistance and the like of the obtained resin are poor; and a largeamount of a toxic gas is generated in a fire.

These known flame-retarding methods for the resins are stillinsufficient and impractical, and they are noticeably limited fortechnical and economical reasons.

The present inventors have intensively investigated to overcome theabove-mentioned drawbacks of the flame-retarding methods for resins, andas a result, it has been found that by using the modified resin or theepoxy-modified resin obtained by the above-mentioned method (A), theflame retardancy can be successfully imparted to the resin. According tothis flame-retarding method of the resin, the modified resin is used inwhich a flame retardancy-imparting component is introduced and bonded tothe resin, and therefore the dispersion and miscibility of the componentcan be achieved without any failure, whereby the flame retardancy of theresin can be remarkably improved; sublimation, bleeding and the like donot-appear in contrast to the method which comprises adding aflame-retardant such as melamine; the production of char is extremelygood, so that the sagging or dripping of oil droplets or a melt can besufficiently inhibited; a toxic gas is scarcely generated; the excellentcharacteristics and physical properties of the resin are not impaired;even to the resin to which the flame retardancy-imparting component isscarcely introduced and bonded in a manufacturing process, thefunctional group regarding the flame retardancy-imparting component canbe easily introduced and bonded; such a functional group can beintroduced after the manufacture of the resin, and so the resin can beeasily manufactured at a low cost. In consequence, an excellentflame-retarding method of a resin can be provided. In addition, it hasalso been found that when the above-mentioned modified resin is usedtogether with phosphoruses, an isocyanuric acid, a cyanuric acid or anamino group-containing compound, the resin having the further improvedflame retardancy can be successfully obtained. In consequence, a moreexcellent flame-retarding method of a resin can be provided. On thebasis of these findings, the present invention has now been attained.

C. Usually, resins tend to become brittle, or are liable to bring aboutdecomposition or coloring owing to the application of external energysuch as heat or light, or owing to the presence of oxygen or a heavymetal. Thus, the long-term heat resistance and weathering resistance ofthe resins are poor, and stability at heating is bad, so thatmoldability is largely limited. Therefore, in order to improvemoldability and workability, it is necessary to blend the resin withanother resin, and this blending results in the deterioration of thecharacteristics and physical properties of the resin. For this reason,the blending method is limited, though the resin has the excellentcharacteristics. Heretofore, various techniques for improving theblending method have been suggested, but they are still insufficient toovercome the above-mentioned faults. In an extreme case, even theexcellent characteristics of the resin are lost, and some of thesuggested techniques cannot be utilized at all.

As an example of conventional thermal stabilization methods, there hasbeen suggested a thermal stabilization method of a resin compositionwhich comprises adding, to the resin composition, a thermal stabilizersuch as a benzoate, an amine, an arylphosphondiamide, an organicphosphite, a hindered phenol, melamine, benzoguanamine, phthaloguanamineor spiroquanamine (e.g. Japanese Patent Publication No. 47739/1976).

However, the resins obtained by this thermal stabilization methods havethe following drawbacks. That is to say, ultraviolet light resistanceand weathering resistance are poor, and color change also noticeablyoccurs; when molding is carried out at a high temperature, coloring, thecolor change and the like also noticeably occur; a thermal stabilizationeffect is still insufficient; the thermal stabilizer itself easily givesrise to thermal decomposition at the time of the working and the thermalstabilization effect is very low, and for the resin which will besubjected to the high-temperature molding, any effect cannot be exerted;and the effect of the thermal stabilizer is very low owing to dispersionfailures such as the loss and bleeding of the added and mixed thermalstabilizer with time, and in an extreme case, the effect is all lost. Inconsequence, this thermal stabilization method of the resin is stillinsufficient and impractical, and its utilization is noticeably limitedfor technical and economical reasons.

In view of the above-mentioned defects of the thermal stabilizationmethod of the resins, the present inventors have intensivelyinvestigated. As a result, it has been found that by using the modifiedresin or the epoxy-modified resin obtained by bonding and introducingthe specific functional group in accordance with the above-mentionedpreparation method (A), the resin can be successfully thermallystabilized. According to this thermal stabilization method of the resin,ultraviolet light resistance, weathering resistance, thermalstabilization and heat resistance can be noticeably improved; since athermal stabilization-imparting component is bonded and introduced tothe resin, the dispersion and miscibility of the component can beachieved without any failure, and so the effect of the stabilization isvery high; the deterioration of the resin can be inhibited even when theresin is used at a relatively high temperature for a long period oftime, and the resin itself is difficult to decompose even at the hightemperature, so that the long-term heat resistance is excellent; sincethe thermal stabilization-imparting component is scarcely lost, so thatthe thermal stabilization effect scarcely deteriorates, and the handlingproperties, physical properties and characteristics of the resin can besufficiently maintained; the decomposition and deterioration of theresin by ions of a heavy metal such as copper can be remarkablyinhibited; even when molding or working is carried out at a hightemperature, the heat deterioration, coloring and color change of theresin can be inhibited; and temperature for 5% weight reduction of theresin at heating can be remarkably improved, so that the thermalstability and heat resistance of the resin can be sufficiently enhancedand the high-temperature molding or working is extremely easy, and forexample, for polyphenyleneether resins and the like in which thehigh-temperature moldability or workability is noticeably limited by aconventional technique, a moldability improver or the like isunnecessary, with the result that a new material having excellentphysical properties and characteristics can be provided at a low cost.In consequence, an excellent thermal stabilization method of the resinscan be provided. On the basis of the finding of this stabilizationmethod of the resins, the present invention has now been attained.

D. Usually, resins possess excellent characteristics and have beenwidely used in many industrial fields, but as resin modificationtechniques for improving various performances and imparting a newperformance without impairing the characteristics of the resin, variouspolymer alloy formation methods have been suggested.

Heretofore, as the polymer alloy formation method of a resin, there havebeen suggested a method which comprises modifying the resin itself toimpart the performance to the resin, and a method which comprises addinga third component such as a compatibilizer to the resin.

The former method is useful which permits the easy formation of themodified resin having not only excellent compatibility and solubilitybut also the uniform performance. However, this method has somedrawbacks. For example, the modification reaction of the resin isdifficult to carry out, and the characteristics of the modified resintend to deteriorate because of the molecular weight reduction, coloringand color change of the resin at the modification. On the other hand,the latter method has the following disadvantages. That is to say, theheat resistance, weathering resistance, water resistance andcharacteristics of the obtained resin deteriorate owing to the presenceof the contained third component; the manufacturing process of thecompatibilizer is complex, and a manufacturing cost of thecompatibilizer is high; it is difficult to obtain the resin having theuniform performance, because of the dispersion failure of the thirdcomponent; and it is also difficult to obtain the resin having improvedphysical properties and characteristics.

The present inventors have intensively investigated to overcome theabove-mentioned defects of the compatibilization method of a resin, andas a result, it has been found that by using the aforesaid modifiedresin or epoxy-modified resin obtained by the above-mentioned method(A), different kinds of resins; can be successfully compatibilized.According to this compatibilization method of resins, thecompatibilization between different kinds of resins and the solubilityof the resins are excellent; the heat resistance, weathering resistance,water resistance, chemical resistance and the like of the obtained resinare also excellent; and the resin can easily be manufactured at a lowcost. In consequence, an excellent compatibilization method of resinscan be provided. On the basis of this knowledge, the present inventionhas now been attained.

E. Usually, resins are excellent in characteristics such as electricalproperties, mechanical properties and moldability, and so they have beenwidely used in many industrial fields, but with the diversification andenhancement of their applications, it has been strongly desired toimprove the characteristics of resins by combination with a differentkind of material. It has been an industrially important theme to improvesurface properties such as the coating properties on the surface of theresin, the adhesive properties of the resin to another kind of material,wettability, dyeability, water/oil repellency and solvent resistance,and electrical properties such as chargeability and conductivity, and ithas been another theme to develop a coating resin composition and anadhesive resin composition useful for such materials.

Heretofore, as methods for modifying the surface of the resin, there hasbeen suggested a surface modification method utilizing an oxidizingagent and corona discharge, and another surface modification methodwhich comprises adding an additive to the resin. In the former method,since a surface treatment is carried out after the molding or the like,a treatment procedure is noticeably troublesome; it is difficult to dothe surface treatment on molded articles having various shapes; and amodification effect is not practically sufficient. In the latter method,since the additive is lost with time, the effect of the additivenoticeably lowers in a short term; and the compatibility of the resinwith the additive as well as the solubility of the additive in the resinis poor, so that the sufficient surface modification effect cannot beobtained. These surface modification methods of the resin are stillpractically insufficient, and the utilization of these methods isnoticeably limited for technical and economical reasons.

The present inventors have intensively investigated with the intentionof overcoming the above-mentioned defects of the surface modificationmethods of a resin, and as a result, it has been found that by using themodified resin or the epoxy-modified resin obtained by theabove-mentioned method (A), the surface of the resin can be successfullymodified. According to this surface modification method of a resin,surface properties such as wettability, coating properties, adhesiveproperties, dyeability, water/oil repellency, and electrical propertiessuch as chargeability and conductivity of the resin can be remarkablyimproved; since the resin itself can be modified, so that the modifiedresin is excellent in high-temperature stability and non-volatility, andthe diminution of the effect due to the loss of a surface-modifyingcomponent does not take place; the surface modification can be uniformlyachieved on molded articles having various shapes; and there can besufficiently modified a polyolefin resin such as a polypropylene resinand a polyolefin fiber in which surface properties such as adhesiveproperties, coating properties and dyeability are noticeably limited. Inconsequence, an excellent surface modification method of a resin can beprovided. In addition, it has also been found that a coating resincomposition and an adhesive resin composition can be provide which areextremely useful for resins and which comprises the above-mentionedmodified resin or epoxy-modified resin. On the basis of these findings,the present invention has now been attained.

OBJECT AND SUMMARY OF THE INVENTION

According to the present invention, there can be provided:

(a) A method for preparing a modified resin which comprises the step ofreacting, in a temperature range of from 200° to 450° C., a resin withat least one selected from the group consisting of compounds each havingat least one norbornenyl group represented by the formula (1) ##STR1##wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈ and R₉ each is a hydrogen atom,an alkyl group having 1 to 4 carbon atoms or a phenyl group, and theymay be the same or different; and Y is a group selected from the groupconsisting of a triazinyl group which may have a substituent, an amidogroup, a carboxylate group, an oxazolinyl group, an oxycarbonyl group,an urethane group, a cyanuric acid ester group, an ether group, acarbamoyl group and a carbonyl group.

(b) The method for preparing a modified resin according to theabove-mentioned paragraph (a) wherein the compound having thenorbornenyl group of the formula (1) is a compound represented by theformula (2) ##STR2## wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈ and R₉ havethe same meanings as defined in the formula (1); R₁₀, R₁₁, R₁₂ and R₁₃each is a hydrogen atom or a group having one or more carbon atoms, andthey may be the same or different.

(c) The method for preparing a modified resin according to theabove-mentioned paragraph (a) wherein the compound having thenorbornenyl group of the formula (1) is a condensate having an averageaddition condensation degree more than 1 which is obtained by subjectinga compound represented by the formula (2) in which at least one of R₁₀,R₁₁, R₁₂ and R₁₃ is a hydrogen atom, a co-condensable compound as anoptional reactant and an aldehyde to addition condensation reaction.

(d) The method for preparing a modified resin according to theabove-mentioned paragraph (a) wherein the compound having thenorbornenyl group of the formula (1) is an etherified condensate havingan average addition condensation degree more than 1 which is obtained bysubjecting a compound represented by the formula (2) in which at leastone of R₁₀, R₁₁, R₁₂ and R₁₃ is a hydrogen atom, a co-condensablecompound as an optional reactant and an aldehyde to addition reaction oraddition condensation reaction, and then subjecting the reaction productand at least one alcohol selected from alcohols having 1-20 carbon atomsto etherification and optionally to simultaneous condensation.

(e) The method for preparing a modified resin according to theabove-mentioned paragraph (a) wherein the compound having thenorbornenyl group of the formula (1) in which Y is an amido group is atleast one selected from the group consisting of reaction products ofamines having one or more carbon atoms and 5-norbornene-2-carbonylhalides.

(f) The method for preparing a modified resin according to theabove-mentioned paragraph (a) wherein the compound having thenorbornenyl group of the formula (1) in which Y is a carboxylate groupis at least one selected from the group consisting of reaction productsof alcohols having four or more carbon atoms and 5-norbornene-2-carbonylhalides.

(g) The method for preparing a modified resin according to theabove-mentioned paragraph (a) wherein the compound having thenorbornenyl group of the formula (1) in which Y is an oxazolinyl groupis :2-(bicyclo 2.2.1!hept-5-en-2-yl)-2-oxazoline.

(h) The method for preparing a modified resin according to theabove-mentioned paragraph (a) wherein the compound having thenorbornenyl group of the formula (1) in which Y is an amido group is atleast one selected from the group consisting of reaction products of acarboxylic acid having one or more carbon atoms and 2-(bicyclo2.2.1!hept-5-en-2-yl)-2-oxazoline.

(i) A method for preparing an epoxy-modified resin which comprises thestep of reacting the modified resin described in any one of theabove-mentioned paragraphs (b) to (d) with at least one selected fromthe group consisting of epoxides.

(j) A flame-retarding method of a resin which comprises the step ofusing at least one resin selected from the group consisting of themodified resins described in the above-mentioned paragraphs (b) to (d)and the epoxy-modified resin described in the above-mentioned paragraph(i).

(k) A thermal stabilization method of a resin which comprises the stepof using at least one refin selected from the group consisting of themodified resins described in the above-mentioned paragraphs (b) to (d)and the epoxy-modified resin described in the above-mentioned paragraph(i).

(l) A compatibilization method of resins which comprises the step ofcompatibilizing at least one resin selected from the group consisting ofthe modified resin described in the above-mentioned paragraph (a) andthe epoxy-modified resin described in the above-mentioned paragraph (i)with one or more other resins.

(m) A surface modification method of a resin which comprises the step ofusing at least one resin selected from the group consisting of themodified resins described in the above-mentioned paragraphs (b) to (d)and the epoxy-modified resin described in the above-mentioned paragraph(i).

(n) A coating resin composition which comprises at least one resinselected from the group consisting of the modified resins described inthe above-mentioned paragraphs (b) to (d) and the epoxy-modified resindescribed in the above-mentioned paragraph (i).

(o) An adhesive resin composition which comprises at least one resinselected from the group consisting of the modified resins described inthe above-mentioned paragraphs (b) to (d) and the epoxy-modified resindescribed in the above-mentioned paragraph (i).

According to the preparation method of the present invention, afunctional group which is excellent in flame retardancy, thermalstability, compatibility, surface modification properties and the likecan be introduced and bonded to a resin without any deterioration of theresin. The utilization of this technique permits obtaining aflame-retardant material having a good char formability, a thermallystable material which can retard the heat deterioration of moldedarticles, a new material which is excellent in miscibility andcompatibility with another resin, a material having a modified surfaceproperties which is excellent in adhesive properties, coatingproperties, wettability and dyeability, a coating resin composition andan adhesive resin composition.

DETAILED DESCRIPTION OF THE INVENTION

A. In a norbornenyl group-containing compound regarding the presentinvention, R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈ and R₉ each in a formula (1)is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or aphenyl group, and they may be the same or different. No particularrestriction is put on the number, position and steric configuration ofthese groups. However, the norbornenyl group-containing compounds inwhich R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈ and R₉ are each selected from thehydrogen atom, a methyl group and the phenyl group are preferable fromthe viewpoints of the availability easiness of raw materials and theeasiness of preparation, purification and the like, and the norbornenylgroup-containing compound in which they are the hydrogen atoms is morepreferable. The norbornenyl group-containing compound has at least onegroup represented by the formula (1), and the number of this group canbe suitably selected in compliance with a use purpose, but it is usuallyin the range of from 1 to 10, preferably 1 to 5, more preferably 1 or 2in consideration of the availability easiness of the compound. When thetwo or more groups of the formula (1) are used, these groups may be thesame or different, but they are preferably the same in view of theavailability easiness of the compound.

Y in the formula (1) is a triazinyl group which may have a substituent,an amido group, a carboxylate group, an oxazolinyl group, an oxycarbonylgroup, an urethane group, a cyanuric acid ester group, an ether group, acarbamoyl group or a carbonyl group, but it is preferably the triazinylgroup which may have a substituent, the amido group, the carboxylategroup or the oxazolinyl group in view of the availability easiness ofraw materials and the impartment of characteristics to an obtainedmodified resin. Particularly, the triazinyl group is preferable.

Typical examples of the norbornenyl group-containing compound regardingthe present invention include 2-(4,6-diamino-1,3,5-triazin-2-yl)-bicyclo2.2.1!hept-5-ene(norbornenecarboguanamine),2-(4,6-diamino-1,3,5-triazin-2-yl)-7-methyl-bicyclo 2.2.1!hept-5-ene,2,-methyl-2-(4,6-diamino-1,3,5-triazin-2-yl)-5-bicyclo 2.2.1!heptene,2-carbamoyl-5-norbornene, N-ethyl-5-norbornene-2-carboxyamide,N-phenyl-5-norbornene-2-carboxyamide,1,6-bis(5-norbornene-2-carboxyamido)hexane,4,4'-bis(5-norbornene-2-carboxyamido)diphenyl ether,1,4-bis(5-norbornene-2-carboxyamido)-benzene, benzoic acid2-(5-norbornene-2-carboxyamido)ethyl ester, 5-norbornene-2-carboxylicacid octyl ester, 5-norbornene-2-carboxylic acid benzyl ester,1,6-bis(5-norbornene-2-carboxylic acid)hexamethylene diester,5-norbornene-2-carboxylic acid methyl ester, 2-methyl-5-bicyclo2.2.1!heptene-2-carboxylic acid butyl ester, 2-(5-bicyclo2.2.1!hepten-2-yl)-2-oxazoline, benzoic acid (5-norbornen-2-yl)ester,isophthalic acid bis(5-norbornen-2-yl)diester,5-norbornene-2-methanolacrylate, 5-bicyclo 2.2.1!hepten-2-yl acetate,2-benzyloxy-5-norbornene, (5-norbornen-2-yl)phenyl ketone,(5-norbornen-2-yl)methyl ketone, 5-norbornene-2-carbonyl chloride,norbornenecarboguanamines represented by the formula (2), theirN-monosubstituted norbornenecarboguanamine derivatives,N,N'-disubstituted norbornenecarboguanamine derivatives,N,N',N"-trisubstituted norbornenecarboguanamine derivatives,N,N',N",N"'-tetrasubstituted norbornenecarboguanamine derivatives,derivatives obtained by reacting 2-hydroxy-5-norbornene,2-amino-5-norbornene and the like with organic isocyanates, carboxylicacids and chlorinated cyanuric acids, addition condensates of thenorbornenecarboguanamines represented by the formula (2) and aldehydes,and etherified condensates obtained by etherifying the additioncondensates and alcohols. Preferable are the compounds represented bythe formula (2), derivatives obtained by reacting5-norbornene-2-carbonyl halides with amines and alcohols, derivativesobtained by reacting 2-(bicyclo 2.2.1!hept-5-en-2-yl)-2-oxazoline withcarboxylic acids such as monocarboxylic acids and dicarboxylic acids,addition condensates of the compounds represented by the formula (2) andaldehydes, etherified condensates obtained by the etherificationreaction of the addition condensates and alcohols. These exemplifiedcompounds are not restrictive.

The norbornenyl group-containing compound regarding the presentinvention can be obtained by a known method. For example, there are amethod which comprises reacting cyclopentadienes which may have an alkylgroup of 1 to 4 carbon atoms or a phenyl group, e.g., cyclopentadiene,dicyclopentadiene, 1-methylcyclopentadiene, 2-methylcyclopentadiene,5-methylcyclopentadiene, methylcyclopentadiene dimer,5-ethylcyclopentadiene, 1-ethyl-3-methylcyclopentadiene,3-isopropyl-1-methylcyclopentadiene, 5-isopropylcyclopentadiene,1,2,3,4-tetraphenylcyclopentadiene, 1,2,4-triphenylcyclopentadiene or1,4-diphenylcyclopentadiene, preferably cyclopentadiene with anunsaturated compound, e.g., (meth)acrylic acid, β-phenylacrylic acid,(meth)acrylic acid ester, vinyl acetate, crotonaldehyde, methyl vinylketone or vinyl phenyl ketone; and a method which comprises subjecting anorbornenyl group-containing compound to hydrogenation reaction,oxidation, reduction reaction, esterification reaction, ester exchangereaction, halogenation or urethane formation reaction. These methods arenot restrictive.

As the norbornenyl group-containing compound in which Y in theabove-mentioned formula (1) is the triazinyl group which may have asubstituent, the compound represented by the formula (2) is particularlyuseful. This compound can be obtained by, for example, a method whichcomprises a ring closing reaction of 2-cyano-5-norbornene anddicyandiamide, or another method which comprises a ring closing reactionof a 5-norbornene-2-carboxylic acid ester and a biguanide. These methodsare very useful.

Furthermore, the norbornenyl group-containing compound in which Y in theabove-mentioned formula (1) is the amido group can be obtained by, forexample, a method using a known amidation reaction of an amine havingone or more carbon atoms and a 5-norbornene-2-carbonyl halide, and thismethod is particularly useful.

Such an amine is preferably a compound having an amino group or an iminogroup of one or more carbon atoms, and example of the amine include, butare not limited to, aliphatic, alicyclic, aromatic and heterocyclicamines such as methylamine, ethylamine, butylamine, octylamine,cyclohexylamine, aniline, hexamethylenediamine,1,4-diaminomethylcyclohexane, 2,5-diaminomethylnorbornane and1,4-diaminobenzene.

The norbornenyl group-containing compound in which Y in theabove-mentioned formula (1) is the amido group can also be obtained by,for example, a method utilizing a known ring opening reaction of acarboxylic acid having one or more carbon atoms with 2-(bicyclo-2.2.1!hept-5-en-2-yl)-2-oxazoline, and this method is also useful.

Examples of the above-mentioned carboxylic acid include, but are notlimited to, aliphatic, alicyclic and aromatic carboxylic acids havingone or more carbon atoms such as propionic acid, cyclohexylcarboxylicacid, benzoic acid, adipic acid and isophthalic acid.

The norbornenyl group-containing compound in which Y in theabove-mentioned formula (1) is the carboxylate group can be obtained bya known method, for example, a method which comprises the esterificationreaction of an alcohol having four or more carbon atoms with a5-norbornene-2-carbonyl halide, or a method which comprises the esterexchange reaction of the above-mentioned alcohol with5-norbornene-2-carboxylic acid methyl ester. These methods are veryuseful.

Examples of this alcohol include, but are not limited to, aliphatic,alicyclic and aromatic alcohols having one or more hydroxy group carbonatoms such as butyl alcohol, hexyl alcohol, cyclohexanol, benzylalcohol, 1,6-hexanediol and 1,4-cyclohexanediol.

Furthermore, the norbornenyl group-containing compound which has thegroup represented by the above-mentioned formula (1) can be obtained bya known method, for example, a method which comprises the reaction of2-hyroxy-5-norbornene with a carboxylic acid or an isocyanate, a methodwhich comprises the reaction of sodium alcoholate of2-hyroxy-5-norbornene and a halogenated alkyl compound or a halogenatedcyanuric acid which may have a substituent, or a method which comprisesthe reaction of a 5-norbornene-2-carbonyl halide and ammonia or anorganic cadmium compound. According to these methods, there can beprovided the norbornenyl group-containing compound in which Y is anoxycarbonyl group, an urethane group, a cyanuric acid ester group, anether group, a carbamoyl group, a carbonyl group or the like.

Particularly preferable examples of the norbornenyl group-containingcompounds regarding the present invention include compounds representedby the formula (2), addition condensates of these compounds andaldehydes, and the etherified condensates obtained by the etherificationreaction of the addition condensate and alcohols. Modified resinsobtained by the use of these compounds are excellent in flameretardancy, thermal stability, compatibility, surface modificationproperties, coating properties, adhesive properties, miscibility withadditives and the like, stickiness to a reinforcing material, dyeabilityand electrical properties; they scarcely bring about color change andquality change at the time of high-temperature working, are excellent inweathering resistance and heat resistance and the like, so that they canmaintain a modification effect for a long period of time; and since theyhave an amino group which is excellent in reactivity, the desireddenaturation or modification can be carried out by reaction with thisamino group.

In the norbornenyl group-containing compound the formula (2)! regardingthe present invention, R₁₀, R₁₁, R₁₂ and R₁₃ are selected from the groupconsisting a hydrogen atom and groups having one or more carbon atoms,and R₁₀, R₁₁, R₁₂ and R₁₃ are the same or different. No particularrestriction is put on the number, position and steric configuration ofthese groups, and useful examples of the groups include aliphatic,alicyclic, aromatic and heterocyclic groups which have one or morecarbon atoms and which may have a functional group or a branched chainsuch as a hydroxyl group, an ester group, an ether group, a carboxylicacid group, a carbonyl group, an amido group, an imido group, a nitrogroup, a sulfonate group, a sulfonamido group, an amino group, an iminogroup or an unsaturated group.

Typical examples of the groups represented by R₁₀, R₁₁, R₁₂ and R₁₃include, but are not limited to, a hydrogen atom, methyl, ethyl,isopropyl, n-butyl, 2-ethylhexyl, octadecyl, allyl, oleyl,4-methylcyclohexyl, phenyl, o-tolyl, α-naphthyl, benzyl, β-phenetyl,o-methoxycarbonylphenyl, p-ethoxycarbonylphenyl, methoxymethyl,butoxymethyl, stearyloxymethyl, 4-methoxyphenyl, tetrahydrofurfuryl,2-(1-piperazinyl)ethyl, 2-(piperazino)ethyl, 2-(morpholino)ethyl,2-(1-pyrrolidinyl)ethyl, 2-pyridinyl, methylol, 2-hydroxyethyl,2-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 12-hydroxydodecyl,1-(2-hydroxyethyl)-2-propenyl, 1-(1-hydroxypropyl)-3-pentenyl,5-hydroxy-3-oxapentyl, 1-(2-hydroxyethyl)-4-oxahexyl,4-hydroxycyclohexyl, 4-hydroxyphenyl, 4-hydroxynaphthyl,4-(hydroxymethyl)phenyl, 2-(4-hydroxyphenyl)ethyl, 3-hydroxypyridin-2-yland 8-hydroxyquinolin-4-yl.

Typical examples of the norbornenyl group-containing compound theformula (2)! regarding the present invention include, but are notlimited to, 2-(4,6-diamino-1,3,5-triazin-2-yl)-bicyclo 2.2.1!hept-5-ene,2-(4,6-diamino-1,3,5-triazin-2-yl)-3-methyl-bicyclo 2.2.1!-hept-5-ene,2-(4,6-diamino-1,3,5-triazin-2-yl)-7-methyl-bicyclo 2.2.1!hept-5-ene,2-(4,6-diamino-1,3,5-triazin-2-yl)-3-phenyl-bicyclo 2.2.1!hept-5-ene,2-(4,6-diamino-1,3,5-triazin-2-yl)-7-isopropyl-bicyclo 2.2.1!hept-5-ene,2-(4,6-diamino-1,3,5-triazin-2-yl)-4-ethyl-6-methyl-bicyclo2.2.1!hept-5-ene,2-(4,6-diamino-1,3,5-triazin-2-yl)-1,4-diphenyl-bicyclo2.2.1!hept-5-ene, their N-mono(di/tri/tetra)-substitutednorbornenecarboguanamines such asN-hydroxymethyl-norbornenecarboguanamine,N-hydroxymethyl-3-methyl-norbornenecarboguanamine,N-(2-hydroxyethyl)-norbornenecarboguanamine,N-(5-hydroxy-3-oxapentyl)-norbornenecarboguanamine,N-methoxymethylnorbornenecarboguanamine,N-butoxymethyl-norbornenecarboguanamine,N-stearyloxymethyl-norbornenecarboguanamine,N-ethyl-norbornenecarboguanamine, N-octyl-norbornenecarboguanamine,N-cyclohexyl-norbornenecarboguanamine,N-phenyl-norbornenecarboguanamine,N-(2-morpholinoethyl)norbornenecarboguanamine, addition condensates ofthe compounds represented by the formula (2) and aldehydes, andetherified condensates obtained by the etherification reaction of theaddition condensate and alcohols.

Examples of the aldehydes, which can be used for the preparation of theN-substituted norbornenyl group-containing compounds represented by theabove-mentioned formula (2) and their condensates, include formaldehydessuch as formaldehyde, paraformaldehyde, hexamethylenetetramine,methylhemiformal, butylhemiformal and formaldehyde-sodium bisulfateadduct, glyoxal, acetaldehyde, trimethylolacetaldehyde, acrolein,benzaldehyde, furfural, phthalaldehyde and terephthalaldehyde, and aboveall, the formaldehydes and glyoxal are preferable and an aqueousformaldehyde solution and paraformaldehyde are more preferable. They arenot restrictive. The amount of the aldehyde to be used is usually in therange of from 0.5 to 20 mols, more preferably 0.7 to 10 mols per mol ofan amino compound comprising the norbornenyl group-containing compoundthe formula (2)! and if necessary, a co-condensable compound.

As the above-mentioned alcohols which can be used for the etherificationreaction in the preparation of these condensates, useful are saturatedand unsaturated aliphatic alcohols having 1 to 20 carbon atoms,alicyclic alcohols, alcohols having an ether group and alcohols havingan aromatic group. Examples of these alcohols include, but are notlimited to, methyl alcohol, isopropyl alcohol, n-butyl alcohol,tert-butyl alcohol, 2-ethylhexyl alcohol, n-nonyl alcohol, n-octadecylalcohol, n-eicocyl alcohol, cyclohexyl alcohol, cyclohexenyl alcohol,4-methylhexyl alcohol, ethylene glycol monomethyl ether, propyleneglycol monoisopropyl ether, diethylene glycol monomethyl ether andbenzyl alcohol.

The use ratio of the norbornenyl group-containing compound the formula(2)! in the condensate regarding the present invention can be suitablyselected in consideration of the desired performance, but in order toaccomplish a good solubility and dispersibility in the resin and inorder to obtain the modified resin having excellent flame retardancy,thermal stability, compatibility, miscibility with additives, surfacemodification properties, coating properties, adhesive properties,dyeability, electrical properties, moldability, solvent resistance,weathering resistance, impact resistance, wear resistance and the like,the amount of the norbornenyl group-containing compounds to be used ispreferably 40 wt % or more, more preferably 60 wt % or more based on theweight of an amino compound comprising the norbornenyl group-containingcompound the formula (2)! and if necessary, the co-condensable compound.

In the preparation of the condensate, the co-condensable compound can beused on occasion as described above, and examples of the co-condensablecompound include, but are not limited to, melamine, N-methylmelamine,benzoguanamine, acetoguanamine, cyclohexanecarboguanamine,cyclohexenecarboguanamine, norbornanecarboguanamine, CTU-guanamine,adipoguanamine, dicyandiamide, urea, alkylurea, thiourea, alkylthiourea,guanidine, urethane, phenol, p-methylphenol, nonylphenol, resol,aniline, tetramethylenediamine, furfural, furfuryl alcohol,p-toluenesulfonamide, o-toluenesulfonamide, benzenesulfonamide,tetralinsulfonamide, carboxylic acid amide, sulfuryl amide and diamidephosphorus nitride low polymer. The amount of the co-condensablecompound to be used should be such as not to impair the significance ofthe norbornenyl group-containing compound the formula (2)!, and it ispreferably less than 60 wt % in the amino compound.

With regard to the formation of the N-methylol compound of theabove-mentioned norbornenyl group-containing compound the formula (2)!,its formation reaction promptly and smoothly proceeds under conditionsof pH of 8.0 to 13.0, preferably 8.5 to 11.5 and a reaction temperatureof 30° C. or more, preferably 40° to 80° C. in a solvent, if necessary,in the presence of a basic compound, to obtain the compound having atleast one HOCH2 group. When the N-methylol compound containing themethylol group at a high content is intended, the reaction is carriedout decreasing the amounts of water and an alcohol to obtain the desiredcompound in a high purity and a high yield. However, if the amounts ofwater and the alcohol are excessively decreased, the deterioration of astirring effect and the nonuniform state of a reaction temperature takeplace, thereby impeding the smooth reaction inconveniently. In order tosmoothly accomplish the reaction, it is useful to suitably employ amethod which comprises carrying out the reaction in the presence of asolvent which is substantially insoluble in water and does not disturbthe reaction, for example, an aromatic hydrocarbon, an aliphatichydrocarbon, a halogenated hydrocarbon or an aliphatic ether, or anothermethod which comprises adding 0.01 to 10 mol % of an auxiliary of. anamine such as an alicyclic amine, an aliphatic amine, an aromatic amineor ammonia to an aldehyde. These methods are not restrictive.

The etherified compound of the above-mentioned norbornenylgroup-containing compound the formula (2)! can be obtained by, forexample, an etherification reaction of the above-mentioned N-methylolcompound at a temperature of 40° to 80° C. for 1 to 8 hours under acidicconditions of a pH 2 to 4 in the presence of the above-mentionedalcohol. In this case, it is particularly preferable that a watercontent in the reaction system is as low as possible and the molar ratioof the alcohol per mol of the N-methylol compound is 10 mols or more.

No particular restriction is put on a method for obtaining thecondensate regarding the present invention, but for example, thecondensate can be obtained by stirring and mixing the above-mentionedamino compound and aldehyde in one or more solvents of water, analcohol, an aromatic compound and the like, and then reacting them at atemperature of 40° to 100° C. under conditions of pH 8.0 or less or pH13.0 or more.

The above-mentioned etherified condensate can be obtained by, forexample, carrying out an etherification reaction or simultaneouslycarrying out the etherification reaction and a condensation reaction ofthe above-mentioned N-methylol compound or its condensate in thepresence of the above-mentioned alcohol at a temperature of 50° to 120°C. under acidic conditions of pH 1.0 to 5.0. This method is notrestrictive.

Condensates, cured compounds and polymer fine particles having anincreased condensation degree are also similarly useful, which can eachbe obtained by treating the above-mentioned norbornenyl group-containingcompound the formula (2)!, its condensate and the etherified condensatewith a curing agent, for example, a mineral acid, a carboxylic acid, asulfonic acid, its ammonium salt, or a compound capable of releasing orforming protons under conditions for the manufacture such as an aqueousmetallic salt of a metal and an acid such as nitric acid, sulfonic acidor phosphoric acid.

In the preparation method of the present invention, the amount of theabove-mentioned norbornenyl group-containing compound to be used isusually in the range of from 0.01 to 60 wt %, preferably from 0.01 to 40wt % based on the weight of the resin, depending upon an applicationpurpose and the like. Even if the norbornenyl group-containing compoundis used in large quantities, the modified resin scarcely gives rise tothe deterioration and change of physical properties such as coloring andthe noticeable decrease of molecular weight. Thus, the method forpreparing modified resins can be considered to be extremely useful inmany fields.

The preparation method of the aforesaid modified resin regarding thepresent invention can be carried out by reacting a resin with theabove-mentioned norbornenyl group-containing compound in a temperaturerange of from 200° to 450° C., but this temperature range depends uponthe kind of selected norbornenyl group-containing compound. When atleast one of the norbornenyl group-containing compounds mentioned in theabove-mentioned paragraphs (b) to (h) is used, the reaction is done in atemperature range of from 230° to 450° C., preferably from 240° to 400°C., more preferably from 250° to 400° C. If one of the norbornenylgroup-containing compounds mentioned in the above-mentioned paragraphs(b) to (h) is used and the reaction temperature is less than 230° C.,the reaction rate is noticeably low and yield is also noticeably low.The upper level of the reaction temperature is such as scarcely to bringabout the deterioration and the like of the resin, and so the uppertemperature is usually 450° C., preferably 400° C. or less. Even if thereaction temperature is in excess of a use temperature range at the timeof the kneading or molding of the material resin, the modified resinscarcely gives rise to quality change such as heat deterioration,coloring and the like by virtue of the extremely excellent thermalstability and heat resistance which the modified resin has. Inconsequence, the reaction can be advanced in the good yield, so that themodified resin having excellent characteristics and physical propertiescan be obtained.

The above-mentioned reaction can be carried out in the presence orabsence of a solvent, and therefore the solvent can be suitably selectedand used in consideration of manufacturing conditions, raw materials andthe like. Nevertheless, it is preferable that the reaction is done inthe absence of the solvent.

No particular restriction is put on the procedure of the reaction, andeither of a batch reaction system and a continuous reaction system isacceptable. A known solution method, molting method, reactive processingmethod in which the reaction is done in the working step of the resin,and the like are applicable, and from these methods, suitable one can beselected. Nevertheless, a certain method is preferable which compriseskneading the resin and the norbornenyl group-containing compound in theabsence of a solvent in a nitrogen atmosphere by a machine for kneadingsuch as a kneader, a single screw extruder, a twin-screw extruder,heating rolls or a Bumbury's mixer, and then extruding the mixture afterthe reaction has finished or while the reaction is proceeding. Accordingto this preferable method, the reaction can be accomplished in anextremely short time without requiring any complex step, and theextrusion can also be done by one step to obtain the continuously anduniformly modified resin.

The above-mentioned reaction can be suitably accomplished underatmospheric pressure, under spontaneously generated pressure in a sealedcontainer, under applied pressure or under reduced pressure, but it ispreferable that for the removal of a gas such as cyclopentadienesgenerated during the reaction, a vent or the like is disposed and thereaction is done under the atmospheric pressure or reduced pressure.

In the preparation method of the present invention, the addition of areaction catalyst, an initiator or the like is not required, but anorganic peroxide such as benzoyl peroxide, lauroyl peroxide or dicumylperoxide can be suitably selected and added as the initiator, ifnecessary, so far as the significance of the present invention is notimpaired. However, the employment of the initiator tends to bring aboutthe deterioration of electrical properties and mechanical properties dueto the decrease of the molecular weight of the resin, and the decline ofheat deterioration, color change, quality change, heat resistance andthermal stability, and for this reason, the use of the initiator isnoticeably limited and so no initiator is preferable. The preparationmethod of the present invention permits the modification of the resinwithout requiring the addition of the initiator, so that this method isnot accompanied with the above-mentioned defects attributable to the useof the initiator. Hence, the preparation method of the present inventioncan be considered to be very excellent.

As the resin regarding the present invention, any resin is usable, sofar as it has a hydrocarbon group. In view of molecular weight, theresins range from high-molecular weight materials such as usual resinsand rubbers to low-molecular weight materials such as waxes and oils,and in view of melting viscosity and Mooney viscosity, the resins rangefrom high-viscosity materials to low-viscosity materials. Thus, theresin can be suitably selected in compliance with an application purposein consideration of these characteristics. According to the preparationmethod of the modified resin of the present invention, the modificationcan be achieved by introducing and bonding the necessary amount of afunctional group which can scarcely be introduced and bonded at the timeof the manufacture of the resin, and therefore this preparation methodis particularly useful for high-molecular weight materials such as usualresins and rubbers as well as resins having no functional group, forexample, polyolefin resin, olefin thermoplastic elastomers such asethylene-propylene rubbers (EP rubbers), ethylene-propylene-dieneterpolymer (EPDM) and ethylene oxide rubber (EOR),hydrocarbon-containing synthetic waxes, and hydrocarbon oils.

Examples of the useful resins regarding the present invention includethermoplastic resins, thermosetting resins, rubbers, blends thereof,block copolymers, graft copolymers, modified resins such asrubber-modified polymers, natural resins, waxes, oils and the like.

Typical examples of these resins include, but are not limited to, usualresins, for example, thermoplastic resins such as polystyrene resinssuch as polystyrene, copolymers and terpolymers of styrene and othermonomers e.g., maleic anhydride, α-methylstyrene, butadiene,acrylonitrile and (meth)acrylic esters, rubber-modified polystyrenes,rubber-modified styrene-acrylonitrile copolymers and rubber-modifiedstyrene-maleic anhydride copolymers; polyolefin resins such aspolyethylene, polypropylene, polybutylene, poly-3-methylbutene,ethylene-vinyl acetate copolymers, ethylene-propylene copolymers andEPDMs; (meth)acrylic resins such as polymethyl acrylate and polymethylmethacrylate; polyamide resins such as nylon 4, nylon 6, nylon 12, nylon66, nylon 612 and copolymerized nylons; saturated polyester resins suchas polyethylene terephthalate and polybutylene terephthalate;polyphenyleneether resins such as poly(2,6-dimethyl-1,4-phenylene)ether,poly(2-methyl-6-ethyl-1,4-phenylene)ether,poly(2-methyl-6-chloro-1,4-phenylene)ether,poly(2-methyl-6-hydroxyethyl-1,4-phenylene)ether, copolymers of2,6-dimethylphenol and 2,3,6-trimethylphenol, end-capped polyphenyleneether resins thereof and resins obtained by modifying them with thestyrene resins and the polyamide resins; polyacetal resins, polyvinylchloride, polyvinylidene chloride, chlorinated polyethylene, chlorinatedpolypropylene, chlorinated rubber, copolymers and terpolymers of vinylchloride and other monomers e.g., vinyl acetate, ethylene, propylene,styrene, isobutylene, vinylidene chloride, maleic anhydride,acrylonitrile, butadiene, isoprene, chlorinated propylene and(meth)acrylic esters!, polyvinyl bromide, brominated polyethylene,polyvinyl fluoride, polyvinylidene fluoride,tetrafluoroethylene-propylene resins, fluorinated resins, vinyl acetateresin, polyamideimides, polyimide resins, polyetherimides, polyphenylenesulfide resins, polyethersulfones, polysulfone resins,polyamine-sulfones, polycarbonates, liquid crystal (polyester) polymers,cyclic polyolefins, polyether ether ketone, polyarylates, phenoxyresins, silicone resins and blends of these resins, block copolymers,graft copolymers and rubber-modified polymers of these resins;thermosetting resins such as diallyl phthalate resins such as diallylphthalate and diallyl-2,6-naphthalene dicarboxylate; unsaturatedpolyester resins such as maleic acid (fumaric acid)-containingpolyester-styrene resins; urethane resins, epoxy resins, siliconeresins, phenol resins, furan resins, amino resins, blends of theseresins and resins obtained by modifying these reins with rubber or thelike; petroleum resins, dicyclopentadiene (DCPP) resins, natural resinssuch as cellulose powder, cellulose acetate, carboxymethyl cellulose,hydroxyethyl cellulose, methyl cellulose, polyglutamic acid andpolyterpene; and modified resins thereof.

In addition, typical examples of the resins include, but are not limitedto, rubbers, for example, synthetic rubbers such as styrene-butadienerubbers (SBRs), butadiene rubbers (BRs), isoprene rubbers (IRs), EPrubbers, EPDM rubbers, acrylonitrile-butadiene rubbers (NBRs), EORs,chloroprenes, butyl rubbers (IIRs), urethane rubbers, silicone rubbers,polysulfide rubbers, hydrogenated nitrile rubbers, polyether rubbers,fluorinated rubbers, telrafluoroethylene-propylene rubbers, acrylicrubbers, chlorosulfonated polyethylene rubbers, epichlorohydrin rubbers,propylene oxide rubbers, ethylene-acrylic rubbers, liquid rubbers,norbornene rubbers, thermoplastic elastomers such as styrene-containingthermoplastic elastomers, olefin-containing thermoplastic elastomers,urethane-containing thermoplastic elastomers, polyester-containingthermoplastic elastomers, polyamide-containing thermoplastic elastomers,1,2-polybutadiene-containing thermoplastic elastomers, vinylchloride-containing thermoplastic elastomers and fluorine-containingthermoplastic elastomers, natural rubbers; waxes, for example, paraffinwaxes, microcrystalline waxes, polyethylene waxes such as Mitsui HighWaxes 800P, 400P, 100P, 410P, 220P, 110P, NL800, NL500 and NL100 MitsuiPetrochemical Industries, Ltd.!, polypropylene waxes such as Mitsui HighWaxes NP055, NP105 and NP805 Mitsui Petrochemical Co., Ltd.!, syntheticwaxes such as Fischer-Tropsch waxes, natural waxes such as carnauba wax,sugarcane wax, palm wax, Japan wax, bees wax, spermaceti and montan wax;oils such as hydrocarbon oils, silicone oils, lubricating oils, naturaloils and fats, blends thereof, and modified substances thereof.

According to the preparation method of the present invention, a variousfunctional group can be introduced into the resin, and therefore theresin which has been modified by the above-mentioned method can befurther subjected to a modification reaction to further advance themodification. The modified resin obtained by the use of the norbornenylgroup-containing compound represented by the formula (2)! has an activeamino group which is excellent in reactivity, and the modification ofthe resin can further be advanced by a modification reaction with analdehyde, an epoxide, a carboxylic acid (anhydride), an isocyanate, anoxazoline, a silane or a silane coupling agent, preferably the epoxide,whereby various kinds of excellent materials can be suitably provided.

According to a method for preparing an epoxy-modified resin regardingthe present invention, the modified resin obtained by the use of theabove-mentioned norbornenyl group-containing compound the formula (2)!is reacted with an epoxide under specific reaction conditions to obtainthe epoxy-modified resin, which can be easily manufactured and in whichsurface properties such as coating properties, adhesive properties,wettability, dyeability, water/oil repellency, solvent resistance andstickiness to a reinforced material are noticeably improved;compatibility with and dispersibility in another resin are furtherimproved; high-temperature stability and non-volatility are excellent,and so the generation of sublimation and breeding is inhibited; and anew material having improved physical properties can be provided as acompatibilizer for different resins. In consequence, the excellentmodification method of a resin can be provided.

No particular restriction is put on the kind of epoxide regarding thepresent invention, and compounds having an aliphatic group, an alicyclicgroup and a heterocyclic group can widely be used, so far as each ofthese compounds has one or more epoxy groups.

Typical examples of the epoxide include, but are not limited to,bisphenol type epoxy resins such as bisphenol A, bisphenol F,halogenated bisphenol A's, cresolnovolak type epoxy resins,phenolnovolak type epoxy resins, phenolnovolak type halogenated epoxyresins and naphthalene type epoxy resins, α-olefin epoxides having 1 to40 carbon atoms, cyclohexene oxide, cyclopentadiene monoxide, butadienedioxide, epoxidized linseed oil, styrene epoxide, methyl glycidyl ether,butyl glycidyl ether, allyl glycidyl ethers, phenyl glycidyl ethers,alkylphenyl glycidyl ethers, 4,4-di(1,2-epoxyethyl)diphenyl ether,diglycidyl ether of resorcin, diglycidyl ether of phloroglucinol,triglycidyl ether of p-aminophenol,tetraglycidyl-bis-(aminophenyl)methane, terephthalic acid diglycidylether, 1,3,5-tri(1,2-epoxyethyl)benzene, 2,2,4,4-tetraglycidoxybenzophenone, hexanediol diglycidyl ether, 2-ethylhexyl glycidyl ether,neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether,polypropylene glycol diglycidyl ether, polyglycidyl ether ofpentaerythritol, vinylcyclohexene dioxide,3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, alicyclicepoxy resins such as trade names "Seroxide #2000", "Seroxide #2021","Seroxide #3000", "Seroxide #4000" made by Daisel Ltd., trade names"Epicoat #1100L" made by Yuka Shell Epoxy Co., Ltd., aromaticamine--containing digycidyl ethers, hydantoin epoxy resin, hetrocyclicepoxy resins such as triglycidyl isocyanurate, polymers of epoxygroup-containing vinyl monomers such as gycidyl(meth)actylate andcopolymerizable compounds, and epoxy group-containing resins obtained bymodifying polyphenyleneether resins, polyamide resins, polypropyleneresins and saturated polyester resins with epichlorohydrin or glycidol.

The amount of the epoxide regarding the present invention can besuitably selected, but it is such that the epoxy group in the epoxide isusually in the range of from 0.1 to 5.0 equivalents, preferably from 0.2to 3.0 equivalents per equivalent of an amino group which bonds totriazine ring in the above-mentioned modified resin.

The preparation method of the epoxy-modified resin regarding the presentinvention is carried out by thermally reacting the modified resinobtained by the above-mentioned method with the epoxide, but thetemperature of the thermal reaction is 150° C. or more, preferably inthe range of from 150° to 400° C., more preferably from 150° to 350° C.If the reaction temperature is less than 150° C., the reaction isnoticeably slow and yield is unpreferably low. Therefore, the reactiontemperature should be 150° C. or more. Moreover, the reactiontemperature should be within the range in which the resin scarcelydeteriorates, and the reaction is usually done at a temperature of 350°C. or less.

The above-mentioned reaction can be suitably carried out by a solutionmethod, a latex method, a melting method, a reactive processing or thelike, as in the preparation method of the modified resin. Nevertheless,a certain method is preferable which comprises kneading the modifiedresin and the epoxide continuously in the same system as in thepreparation of the modified resin after the preparation of the modifiedresin in the absence of a solvent by a single screw extruder, atwin-screw extruder, heating rolls, a Bumbury's mixer or a kneader, andthen extruding the mixture after the reaction has finished or while thereaction is proceeding. This preferable method has the same excellentpoints as described above.

In the preparation method of the epoxy-modified resin, a reactionaccelerator can be suitably selected and used, and examples of thereaction accelerator include a metallic salt of an organic acid such astin octylate, imidazoles and novolak type phenol resins.

The modified resins and the epoxy-modified resins regarding the presentinvention are excellent modification and improvement in physicalproperties such as flame retardancy, thermal stability, heat resistance,impact resistance, high strength and high elasticity, resincompatibility, flexing resistance and fatigue resistance, wearresistance, tear resistance, dimensional stability, stress relaxation,vibration-damping properties, heat resistance and cold resistance,solvent resistance (oil and water), weathering resistance, gloss,refractive index change, self-lubrication, plasticity and gas barrierproperties as well as adhesive properties, stickiness to a reinforcingmaterial such as a glass fiber, sliding properties, plating properties,coating properties with a paint or the like, dyeability of a resin orits fiber, blocking resistance, electrical properties such as electricalinhibition properties, conductivity, static properties and trackingresistance, fluidity, retraction, heat fusion strength, flowmoldability, crystallinity, orientation, operating characteristics suchas moldability or workability, and economical properties such as savingof resources and substitution for resources. Therefore, the modifiedresins and the epoxy-modified resins of the present invention areindustrially very useful in a wide range as construction materials,interior decorations, housewares such as bathtubs and toilets, interiordecorations and exterior decorations for vehicles, e.g., cars such asinstrument panels, pillars, meter clusters, door trims, armrests,defroster garnishes, console boxes, pocket decks, bumpers, side sillgarnishes, cowl top garnishes, wheel covers, spoilers and head lampinner panels, reinforcing and molding materials such as long and shortglass fibers, electrical materials such as resist materials andelectrically insulating materials, electrophotographic materials such astoners, fibrous materials, fiber and paper making materials, paints forcars and appliances, antifouling and anticorrosive paints, powderedpaints, traffic paints, adhesives such as hot-melt adhesives, tackifyingresin and adhesives for structures such as industrial articles, ICsealing compounds, rubber modifiers, optical materials, leather treatingsolutions, agricultural materials, medical instruments, packingmaterials, equipments for foods such as containers, fibers such astents, cloths and wear, mechanical equipments such as gears andpackings, antifouling and anticorrosive equipments such as pipes andtanks, heat-resistant equipments, warmth keeping materials and coldkeeping materials, oil modifiers, flame-retardants, surface activeagents, rust preventives, antioxidants and the like.

B. In the flame-retarding method of a resin regarding the presentinvention, at least one of the modified resins described in theabove-mentioned paragraphs (b) to (d) and the epoxy-modified resindescribed in the above-mentioned paragraph (i) can be used in a suitableamount, and the modified resin may occupy a total portion or a partialportion of the resin. Practically, the modified resin is used in such anamount that the content of a triazine nucleus in the resin is in therange of from 2 to 40 wt %, preferably from 4 to 30 wt %. If the contentof the triazine nucleus is less than 2 wt %, a sufficient flameretardancy effect can scarcely be obtained, and if it is more than 40 wt%, the moldability of this resin is poor, and the deterioration of theresin occurs inconveniently to lower physical properties.

In the flame-retarding method of a resin, it is particularly preferableto additionally use at least one component selected from phosphorusesconsisting of simple substances of phosphorus and phosphorus-containingcompounds together with the modified resin regarding the presentinvention in the resin. This reason is that the phosphoruses can exert asynergistic effect that a flame-retarding effect can be furtherimproved. This excellent synergistic effect is believed to be not onlydue to the easy formation of a flame retardant film having a relativelylow volatility on a burning resin surface but also due to theacceleration of char formation to increase a char layer so that oxygencan be prevented from spreading to the burning surface, the release of aflammable gas from the resin portion can be inhibited, and theconduction of heat to the resin portion can be reduced.

Useful examples of such phosphoruses include, but are not limited to,simple substances of phosphorus such as red phosphorus;phosphorus-containing acids such as phosphoric acid, polyphosphoricacids, phosphorous acid, phosphonic acid, phosphate salts, polyphosphatesalts, phosphite salts and phosphonate salts; phosphate esters such asphosphoric triesters, polyphosphate esters, acidic phosphate esters andsalts thereof; phosphite esters such as phosphorous triesters and acidicphosphorous diesters; phosphonate esters such as phosphonate esters,acidic phosphonate esters and salts thereof; phosphines such asphosphine, phosphine oxide and phosphonium salts; and sulfur-containingphosphorus compounds such as dialkyl thiophosphates and salts thereof.

Examples of the above-mentioned phosphorus-containing acids includeacids such as phosphoric acid, pyrophosphoric acid, tripolyphosphoricacid, polyphosphoric acid, phosphorous acid and phosphonic acid; andsalts obtained by either partially or fully neutralizing these acidswith bases such as ammonia, amines, alkali metals or alkaline earthmetals, namely, ammonium phosphate, ethylenediamine phosphate, sodiumphosphate, calcium phosphate, melamine pyrophosphate, sodiumpyrophosphate, ammonium tripolyphosphate, sodium tripolyphosphate,ammonium polyphosphates, sodium polyphosphates, ammonium phosphite,calcium phosphite and ammonium phosphonate. Above all, ammoniumpolyphosphates represented by the formula (NH₄)_(m) +₂ P_(m) O_(3m+1)(wherein m is an integer more than 5) are preferred. It is however to benoted that the above-mentioned phosphorus-containing acids are notlimited to these examples.

In the above-described ammonium polyphosphates represented by theformula (NH₄)_(m+2) P_(m) O_(3m+1) (wherein m is an integer more than5), it is preferred to set m at a substantially large value so as tomake water solubility smaller in view of the flame retarding effect andthe physical properties of the resulting resin. A salt in which m is aninteger more than 50 is particularly preferred. This salt practicallycorresponds to a metaphosphate (NH₄ PO₃)_(m).

Examples of the ammonium polyphosphates include "Exolit 263" (tradename; made by Hoechst AG), "Exolit 422" (trade name; made by Hoechst AG)and "Phoscheck P/30" (trade name; made by Monsanto Chemical Company).

Examples of the above-mentioned phosphate esters include, but are notlimited to, phosphoric triesters such as trimethyl phosphate,tri-n-butyl phosphate, trilauryl phosphate, tristearyl phosphate,trioleyl phosphate, tris(butoxyethyl) phosphate, triphenyl phosphate,tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate,xylene diphenyl phosphate, tris(isopropylphenyl)phosphate, isopropyldiphenyl phosphate, 2-ethylhexyl diphenyl phosphate, stearyl diphenylphosphate, oleyl diphenyl phosphate, butyl dicresyl phosphate, lauryldicresyl phosphate, diphenyl-2-metacroyloxy ethyl phosphate,tris(2-chloroethyl)phosphate, tris(2-chloropropyl)phosphate,tris(2,3-dichloropropyl) phosphate, tris(2,3-dibromopropyl)phosphate,tris(bromochloropropyl)phosphate and tris(tribromophenyl)phosphate;acidic phosphate esters such as mono/dimethyl acid phosphate,mono/diethyl acid phosphate, monobutyl acid phosphate, di-2-ethylhexylphosphate, mono/dilauryl acid phosphate, mono/distearyl acid phosphate,mono/dioleyl acid phosphate, mono/di-2-chloroethyl acid phosphate,mono/dibutoxyethyl acid phosphate, ethylene glycol acid phosphate,dibutyl pyrophosphate, mono/diphenyl acid phosphate, mono/dicresyl acidphosphate, mono/dixylenyl acid phosphate; ammonia, amine, melamine,alkali metal and alkaline earth metal salts of acidic phosphate esterssuch as ammonium dimethyl phosphate, ammonium ethyl phoshate, ammoniumdi-n-butyl phosphate, triethanolamine dibutoxyethyl phosphate,morpholine dioctyl phosphate, sodium mono-n-butyl phosphate, ammoniumdiphenyl phosphate, melamine diphenyl phosphate, piperazine diphenylphosphate, ammonium phenyl phosphate, ethylenediamine dicresylphosphate, sodium cresyl phosphate and melamine dixylenyl phosphate.

Examples of the above-mentioned phosphite esters include, but are notlimited to, phosphite triesters such as trimethyl phosphite, triethylphosphite, tributyl phosphite, tris(2-ethylhexyl)phosphite, trialurylphosphite, trioleyl phosphite, tristearyl phosphite, triphenylphosphite, tris(nonylphenyl)phosphite,tris(2,4-di-t-butylphenyl)phosphite, tris(dinonylphenyl)phosphite,bis(nonylphenyl)dinonylphenyl phosphite, diphenylmono(2-ethylhexyl)phosphite, diphenyl monodecyl phosphite, diphenylmono(tridecyl)phosphite, phenyl diisooctyl phosphite, tetraphenyldipropylene glycol diphosphite, poly(dipropylene glycol)phenylphosphite, diisodecyl pentaerythritol diphosphite,bis(tridecyl)pentaerythritol diphosphite, distearyl pentaerythritoldiphosphite, bis(nonylphenyl)pentaerythritol diphosphite,bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, phenyl4,4'-isopropylidenediphenyl pentaerythritol diphosphite, tetraphenyltetra(tridecyl)pentaerythritol tetraphosphite,tetra(tridecyl)-4,4'-isopropylidenediphenyl phosphite, hydrogenatedbisphenol A phosphite polymer, pentaerythritol hydrogenated bisphenol Atriphenyl phosphite polycondensate, tetra(tridecyl)-4,4'-n-butylidenebis(2-t-butyl-5-methylphenol)diphosphite, bis(neopentyl glycol)1,4-cyclohexane dimethylene phosphite, bis(octylphenyl)bis4,4'-n-butylidene bis(2-t-butyl-5-methylphenol)!1,6-hexanediol phosphiteand tetra(tridecyl)-1,1,3-tris(2'-methyl-5'-t-butyl-4'-oxyphenyl)butanediphosphite; and phosphite diesters such as dimethyl hydrogenphosphite,dibutyl hydrogenphosphite, di(2-ethylhexyl)hydrogenphosphite, dilaurylhydrogenphosphite, dioleyl hydrogenphosphite and diphenylhydrogenphosphite.

Examples of the above-mentioned phosphonic acids include, but are notlimited to, phosphonate diesters such as dimethyl methylphosphonate,ethyl diethylphosphonoacetate, bis(2-chloroethyl)vinylphosphonate,diethyl N,N-bis(2-hydroxyethyl)aminomethylphosphonate, dibutylbutylphosphonate, di-2-ethylhexyl hydroxymethylphosphonate,di-2-ethylhexyl 2-ethylhexylphosphonate, dimethyl phenylphosphonate,diallyl phenylphosphonate, dioctyl phenylphosphonate and dinaphthylphenylphosphonate; acidic phosphonate esters such as mono-2-ethylhexyl2-ethylhexylphosphonate and monooctyl phenylphosphonate; and phosphonateester salts such as ammonium mono-2-ethylhexyl-2-ethylhexylphosphonate,triethanolamine monooctyl phenylphosphonate, melamine mono-2-ethylhexyl2-ethylhexylphosphonate and sodium monooctyl phenylphosphonate.

Examples of the above-mentioned phosphines include, but are not limitedto, phosphines such as triethylphosphine, tri-n-octylphosphine,tris(2-cyanoethyl)phosphine, tris(3-hydroxypropyl)phosphine,tricyclohexylphosphine, triphenylphosphine, tri-p-tolylphosphine,tri(2,6-dimethoxyphenyl)phosphine, 9-phosphabi-cyclo 3.3.1!,4.2.l!nonane (mixture), bis(1,2-diphenylphosphino)ethane,bis(1,4-diphenylphosphino)butane, diphenyl-p-styrylphosphine,diphenylphosphinous chloride and bis(diphenylphosphino)ferrocene;phosphine oxides such as triethylphosphine oxide, tri-n-octylphosphineoxide, tris(2-cyanoethyl)phosphine oxide, tris(3-carboxyethyl)phosphineoxide, tris(3-hydroxypropyl)phosphine oxide and triphenylphosphineoxide; and phosphonium salts such as tetra-n-butylphosphonium bromide,tri-n-butylallylphosphonium bromide,ethylenebistris(2-cyanoethyl)phosphonium bromide,ethyltriphenylphosphonium bromide, tetraphenylphosphonium bromide,tri-n-octylethylphosphonium bromide, tetra-n-butylphosphoniumO,O-diethylphosphorodithioate, tetrakis(hydroxymethyl)phosphoniumsulfate, tetra-n-butylphosphonium iodide, ethyltriphenylphosphoniumiodide, triethylbenzylphosphonium chloride, tetra-n-butylphosphoniumchloride, tri-n-butyltetradecylphosphonium chloride,tris(2-cyanoethyl)allylphosphonium chloride, benzyltriphenylphosphoniumchloride and bis(triphenylphosphin)iminium chloride.

Examples of the above-mentioned sulfur-containing phosphorus compoundsinclude, but are not limited to, dimethyl phosphorodithioate,di-n-propyl phosphorodithioate, ammonium diethyl phosphorodithioate,melamine di-n-propyl phosphorodithioate, sodium dimethylphosphorodithioate, trilauryl trithiophosphite,tris(lauryl-2-thioethyl)phosphite, diphenyl bis 4,4'-n-butylidenebis(2-t-butyl-5-methylphenyl)!thiodiethanol diphosphite,triphenylphosphine sulfide, tris(2-cyanoethyl)phosphine sulfide andtri-n-butylphosphine sulfide.

In the present invention, the phosphoruses can be used in an amount of 5to 40 wt %, preferably 10 to 30 wt % based on the resin. An amount lessthan 5 wt % cannot bring about the sufficient synergistic effect forimproving the flame retardancy. An amount more than 40 wt %, on theother hand, causes the deterioration of physical properties. Because ofthese disadvantages, the amounts outside the above-mentioned range arenot preferred practically.

In the resin, the phosphoruses may be present separately from thecomponent of the modified resins, or a part or the entire part of thephosphoruses may form a salt with the modified resin. The inclusion of asalt, for example, in the form of a salt of phosphoric acid, apolyphosphoric acid, phosphorous acid, phosphonic acid, acidic ammoniumpolyphosphate, an acidic phosphate ester or an acidic phosphonate esterwith the modified resin is preferred, because of the still bettersynergistic effect for the improvement of the flame retarciancy.

The modified resin of the present invention can further improve theflame retardancy of the resin, when incorporated together with aspecific isocyanuric acids and/or cyanuric acids in the resin as amethod for making the resin retardant to flame. This combination use istherefore preferred.

Examples of the specific isocyanuric acids and cyanuric acids includeisocyanuric acids represented by the formula (3) ##STR3## wherein R₁₄,R₁₅ and R₁₆ may be the same or different and they are individually ahydrogen atom or an alkyl group having 1 to 3 carbon atoms, an oxyalkylgroup having 1 to 3 carbon atoms, a phenyl group or a glycidyl group,and cyanuric acids represented by the formula (4) ##STR4## wherein R₁₄,R₁₅ and R₁₆ have the same meanings as defined in the formula (3).

The isocyanuric acids useful in the practice of the present inventionare the compounds represented by the formula (3) in which R₁₄, R₁₅ andR₁₆ are the same or different and individually represent a substituentselected from the group consisting of a hydrogen atom, an alkyl grouphaving 1 to 3 carbon atoms, an oxyalkyl group having 1 to 3, a phenylgroup and a glycidyl group. Typical examples of such isocyanuric acidsinclude, but are not limited to, isocyanuric acid, methyl isocyanurate,trimethyl isocyanurate, triethyl isocyanurate,tris(2-hydroxyethyl)isocyanurate, phenyl isocyanurate, diphenylisocyanurate, triphenyl isocyanurate, dimethyl phenyl isocyanurate andtriglycidyl isocyanurate.

The cyanuric acids useful in the practice of the present invention arecompounds represented by the formula (4) in which R₁₄, R₁₅ and R₁₆ havethe same meanings as defined in the formula (3). Typical examples ofsuch cyanuric acids include, but are not limited to, cyanuric acid,methyl cyanurate, trimethyl cyanurate, triethyl cyanurate,tris(2-hydroxyethyl)cyanurate, phenyl cyanurate, diphenyl cyanurate,triphenyl cyanurate, dimethyl phenyl cyanurate and triglycidylcyanurate.

In the present invention, the use ratio (an equivalent ratio to thetriazine nucleus) of the sum of the isocyanuric acids and the cyanuricacids to the triazine nucleus equivalent in the modified resin can rangefrom 0.01 are 5, preferably from 0.1 to 3. Use ratios less than 0.01 aretoo small to sufficiently bring about the effect of their combinationuse, whereas use ratios more than 5 lead to the deterioration ofphysical properties. The use ratios outside the above range aretherefore not preferred from the practical viewpoint.

In the resin, such isocyanuric acids and cyanuric acids may presentseparately from the modified resin, or a part or the entire part ofthese acids may form salts and/or react with the modified resin and mayhence be contained partially or entirely in the form of salts. Inclusionof a salt and/or product, for example, a salt of an isocyanuric acidwith the modified resin and a reaction product of triglycidyl cyanuratewith the modified resin can bring about the still better flame-retardingeffect, heat resistance and the like and is hence preferred.

Useful examples of the above-mentioned salt include, but are not limitedto, a salt obtained by dissolving or dispersing the isocyanuric acid andthe modified resin in the presence or absence of a solvent and thenheating the resulting solution to react them, a salt obtained byreacting the isocyanuric acid with the modified resin at a ratio of oneto several equivalents of the isocyanuric acid to one equivalent of thetriazine nucleus in the modified resin, and mixtures of the salts formedthrough these reactions.

The above-mentioned modified resin can further improve the flameretardancy of a resin, when employed in accordance with aflame-retarding method for the resin in which the modified resin isincorporated together with an amino-containing compound in the resin.This combination use of the modified resin with the amino-containingcompound is therefore preferred.

The amino-containing compound has an aliphatic group, an alicyclicgroup, an aromatic group or a heterocyclic group having at least twocarbons. Preferred are compounds containing an aliphatic group, analicyclic group or a heterocyclic group having at least two carbons.More preferred are compounds which contain ##STR5## as well asdicyandiamide, guanidine and reaction products between these compoundsand aldehydes such as formaldehyde or epoxy compounds.

Typical examples of such amino-containing compounds include, but are notlimited to, 1,2-ethylenediamine, 1,3-diaminopropane, 1,2-diaminopropane,1,4-butylenediamine, 1,6-hexamethylenediamine, polyalkylenepolyaminessuch as diethylenetriamine, triethylenetetramine, tetraethylenepentamineand pentaethylenehexamine, cyclohexylamine, cyclohexyldiamine,1,3-bis(aminomethyl)cyclohexane, aniline, benzylamine, furfurylamine,N-(3-aminopropyl)morpholine, N-(2-aminoethyl)morpholine,N-(2-aminoethyl)-piperazine, N-(3-aminopropyl)piperazine,N-(2-aminoethyl)piperidine, N,N'-bis(2-aminoethyl)piperazine,dicyandiamide, guanidine, urea and polyamide resins and reactionproducts between these compounds and aldehydes such as formaldehyde, forexample, ethylenediamine-formaldehyde (1/1) reaction product,piperazine-formaldehyde (1/1) reaction product, pentamethylene-hexamineand salts thereof.

In the present invention, the amino-containing compound can be used inan amount of 0.01 to 10 wt %, preferably 0.05 to 5 wt % based on theresin. Amounts less than 0.01 wt % cannot exhibit synergistic effect tosufficient extent for the improvement of the flame retardancy, whereasamounts more than 10 wt % lead to the deterioration of physicalproperties. Amounts outside the above range are therefore not preferredfrom the practical viewpoint.

In the flame-retarding method of the present invention for the resin,the thermal stability and the like of the resin can be improved byadditionally incorporating additives such as a phenolic antioxidant, anamine-base antioxidant, a sulfur-containing antioxidant and a lightstabilizer. These additives can be chosen as needed depending on theapplication purpose.

Examples of the above-mentioned phenolic antioxidant include knowncompounds, for example, monophenolic compounds such as2,6-di-t-butyl-p-cresol, butylated hydroxyanisoles,2,6-di-t-butyl-4-ethylphenol andoctadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, bisphenoliccompounds such as 2,2'-methylene-bis-(4-methyl-6-t-butylphenol),2,2'-methylene-bis-(4-ethyl-6-t-butylphenol),4,4'-thiobis-(3-methyl-6-t-butylphenol) and4,4'-butylidene-bis-(3-methyl-6-di-t-butylphenol), and high-molecularphenolic compounds such as1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane,1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene,tetrakismethylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate!methane, bis3,3'-bis(4'-hydroxy-3'-t-butylphenyl)butylic acid! glycol ester and thelike. They can each be used in an amount of 0.001 to 2.0 wt %,preferably 0.05 to 1.0 wt % based on the resin.

Examples of the above-mentioned amine-base antioxidants include knowncompounds, for example, phenyl-l-naphthylamine, phenyl-2-naphthylamine,N,N'-diphenyl-p-phenylenediamine,6-ethoxy-2,2,4-trimethyl-1,2-dihydroxyquinoline, dioctyliminodibenzyl,diethanolamine, triisopropanolamine, octadecyldiethanolamine,N,N'-diphenylethylenediamine, triethyltetramine, 4 mol ethylene oxideadduct of tridecylamine, 20 mol ethylene oxide adduct of hexadecylamineand the like. They can each be used in an amount of 0.02 to 5.0 wt %based on the resin.

Examples of the above-mentioned sulfur-containing antioxidants includeknown compounds, for example, dilauryl 3,3'-thio-di-propionate,dimyristyl 3,3'-thio-di-propionate, distearyl-3,3'-thio-di-propionate,2-methylmercaptobenzoimidazole, pentaerythritol-tetrakis-(alaurylthiopropionate) and the like. They can each be used in an amount of 0.01to 4.0 wt %, preferably 0.05 to 2.0 wt % based on the resin.

Examples of the above-mentioned light stabilizers include, but notlimited to, known compounds, for example, benzophenone compounds,acetophenone compounds, benzotriazole compounds, benzoate compounds,oxalic anilide compounds, cyanoacrylate compounds, organic nickelcompounds and hindered amine compounds. It is also possible to chooseand use, as needed, one or more of the following additives: nucleatingagents, for example, 4-t-butyl benzoate, adipic acid and diphenylacetate; metal inactivating agents, for example, oxanilide, dicarboxylicdihydrazides and salicylic hydrazide; and free radical promoters, forexample, 2,3-dimethyl-2,3-diphenylbutane (trade name "INTALOX CC DFB",made by Peroxyd Chemie GmbH), 3,4-dimethyl-3,4-diphenylhexane (tradename "INTALOX CC DFH", made by Peroxyd Chemie GmbH) and2,3-dimethyl-2,3-diphenylhexane.

In the flame-retarding method of a resin regarding the presentinvention, no particular limitation is imposed on the manner of theproduction of the resin. It is possible to apply any production methodwhich is generally employed in mixing powdery additives in the resin. Inthe case of a thermoplastic resin or the like, for example, the resin inthe form of pellets or a powder is mixed in advance with the additivesat ordinary temperature and the resulting mixture is molten, mixed andthen molded by an extruder, a heating roll, a kneader or the like. As analternative, a resin containing the additives at high concentrations isbeforehand produced and is then molten and kneaded together with theusual resin, and the resulting mixture is thereafter molded. In the caseof a thermosetting resin or the like, on the other hand, componentsessential to the present invention are added, before curing, to amonomer or prepolymer, or to a dope or compound which has been formed byadding a reinforcing material to the monomer or prepolymer. Theresulting mixture is kneaded and then molded. It is however to be notedthat the practice of the present invention should not be limited tothese production methods.

In the flame-retarding method of a resin regarding the presentinvention, other additives can also be incorporated as needed to extentnot impairing the advantageous effects of the present invention.Examples of these additives include plasticizers, dyes and pigments,dispersants, organic chelating agents, stabilizers, foaming agents,antihazing agents, delustering agents, surface treatments, fluorescentagents, mildewproofing agents, bacteriocides, antioxidants, ultravioletlight absorbers, known flame retardants or flame-retarding aids such asantimony trioxide, barium metaborate, zirconium dioxide, lead oxide,zinc borate, aluminum hydroxide, ammonium salts such as ammonium sulfateand ammonium carbonate, reaction products of cyanuric chloride andamines, and the triazine nucleus-containing compounds such as melaminederivatives, lubricants such as high fatty acids, higher fatty acidesters, higher fatty acid metal salts and bisamides, antistatic agentssuch as sulfonic acids, quaternary ammonium salts, polyhydric alcoholesters, alkylamides, alkylamines and electrically conductive carbonblack, reinforcing materials such as glass fibers and carbon fibers,fillers such as talc, clay, calcined clay, mica, calcium silicate,calcium sulfate, calcium carbonate, glass beads, molybdenum disulfideand graphite, nucleating agents, processing aids, parting agents, andother polymers.

In the flame-retarding method of a resin regarding the presentinvention, it is preferred to additionally incorporate at least oneselected from phosphoruses consisting of simple substances of phosphorusand phosphorus-containing compounds. Preferred phosphoruses are, forexample, red phosphorus, phosphoric acid, polyphosphoric acids,phosphorous acid, phosphonic acid, phosphate salts, polyphosphate salts,phosphite salts, phosphonate salts, phosphate esters, phosphite esters,phosphonate esters, phosphines and sulfur-containing phosphoruscompounds. Particularly preferred polyphosphate slats are ammoniumpolyphosphates represented by the following formula (NH₄)_(m+2) P_(m)O_(3m+1) (wherein m is an integer more than 5). As an alternative, it isalso preferred to additionally incorporate at least one componentselected from the isocyanuric acids and cyanuric acids represented bythe formula (3) and the formula (4), respectively.

As a further alternative, it is also preferred to additionallyincorporate at least one component selected from amino-containingcompounds. Preferred are, for example, compounds containing at least onegroup selected from ##STR6## dicyandiamide, guanidine, and theirreaction products with aldehydes or epoxy compounds.

It is particularly preferred to additionally incorporate theabove-described phosphoruses and amino group-containing compoundtogether as the flame-retarding aids.

The resins to which the flame-retarding method of the present inventioncan be applied are preferably a thermoplastic resin, a thermosettingresin and a thermoplastic elastomer. Preferable examples of thethermoplastic resin include polyolefin resins, polyamide resins,polystyrene resins, polyphenyleneether resins, polyacrylic resins,saturated polyester resins and polycarbonate resins. Preferable examplesof the thermosetting resin include unsaturated polyester resins, diallylphthalate resins, epoxy resins and urethane resins, and preferableexamples of the thermoplastic elastomer include olefin thermoplasticelastomers.

Among the polyolefin resins, the polypropylene resins and polystyreneresins are extremely difficult to flame-retard, and so a conventionaltechnique requires a large amount of an additive such as a triazinecompound or a phosphorus compound to impart the flame retardancythereto. However, because of the poor miscibility of the additive, thephysical properties of the resulting resin product deterioratenoticeably. On the contrary, the employment of the modified resinregarding the present invention permits an aminotriazinyl group to beintroduced and bonded to the resin, whereby the above-mentioneddisadvantages can be overcome sufficiently. For these advantages, theflame-retarding method of the present invention is particularly usefulto these polypropylene resins and polystyrene resins.

C. According to a thermal stabilization method of a resin regarding thepresent invention, at least one of the modified resins described in theabove-mentioned paragraphs (b) to (d) and the epoxy-modified resindescribed in the above-mentioned paragraph (i) is incorporated in theresin. As a result, the heat stability, ultraviolet light resistance,long-term heat resistance and weathering resistance of the resin can beremarkably improved; the excellent molded article of the resin can beprovided which scarcely brings about heat deterioration, coloring andcolor change at high-temperature working; and the aforesaid modifiedresin is excellent in high-temperature stability, non-volatility andhandling properties and can sufficiently protect the resin fromdecomposition or deterioration by heavy metal ions such as copper ions.In consequence, an excellent method for modifying a resin can beprovided.

Furthermore, the temperatures at which the weight of the resin isreduced 1% and 5% by heating can be remarkably improved, and hencehigh-temperature working can be easily done without any trouble, whichpermits various kinds of molding and working operations. For example,polyphenyleneether resins are excellent in thermal physical propertiesat high temperatures, but these resins give rise to decomposition andgelation at the time of the high-temperature molding and working, sothat they are very poor in moldability. Therefore, they are blended withanother resin such as a polystyrene resin to improve the moldability andworkability, with the result that the excellent thermal characteristicswhich they originally have are impaired and in a certain case, thesecharacteristics are not utilized at all. In the aforesaid modified resinregarding the present invention, the heat stability can be remarkablyimproved, and the molding and working at high-temperatures are possible,so that the other resin to be blended can be reduced or is not requiredany more. In consequence, inexpensive new materials having the excellentcharacteristics can be provided.

In the thermal stabilization method of a resin regarding the presentinvention, at least one of the aforesaid modified resins andepoxy-modified resin can be used in a suitable amount, and the modifiedresin may occupy a total portion or a partial portion of the resin.Practically, the modified resin is used in such an amount that thecontent of a triazine nucleus in the resin is in the range of from 0.01to 10 wt %, preferably from 0.02 to 5 wt %. If the content of thetriazine nucleus is less than 0.01 wt %, a sufficient stabilityimprovement effect to heat, light and the like can scarcely be obtained,and on the other hand, if it is more than 10 wt %, the stability effectis not particularly improved any more, which is not preferable from aneconomical viewpoint.

The resins to which the thermal stabilization method of the presentinvention can be applied are substantially the same as theabove-mentioned resins to which the flame-retarding method of thepresent invention is applicable. The thermal stabilization method of theresin regarding the present invention can enhance its stabilityimprovement effect still further, when additives such as theabove-described phenolic antioxidants, amine-base antioxidants,sulfur-containing antioxidants, light stabilizers, nucleating agents andother additives are additionally used in amounts similar to thosespecified above or the below-described phosphite antioxidants are usedadditionally. These additives can be chosen as needed depending on theapplication purpose.

Examples of the phosphite antioxidants include triphenyl phosphite,tris(nonylphenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite,diphenyl decyl phosphite, 2-ethylhexyl diphenyl phosphate, phenyldiisodecyl phosphite, diphenyl acid phosphate, tridecyl phosphate,tris(2-ethylhexyl)phosphite, tributyl phosphite, dilauryl acidphosphite, ditridecyl pentaerythritol diphosphite, distearylpentaerythritol diphosphite, bis(2,4-di-t-butylphenyl)pentaerythritoldiphosphite, bis(nonylphenyl)pentaerythritol diphosphite, diisodecylpentaerythritol diphosphite, phenyl-4,4'-isopropylidenediphenolpentaerythritol diphosphite, trilauryl trithiophosphite,tris(lauryl-2-thioethyl)phosphite, diphenyl bis4,4'-n-butylidenebis(2-t-butyl-5-methylphenol)!thiodiethanoldiphosphite, bis(neopentylglycol)-1,4-cyclohexanedimethylene phosphite,hydrogenated 4,4'-isopropylidenediphenol polyphosphite,bis(octylphenyl)bis4,4'-n-butylidenebis(2-t-butyl-5-methylphenol)!1,6-hexanedioldiphosphite,tetratridecyl-4,4'-n-butylidenebis(2-t-butyl-5-methylphenol)diphosphite,tetratridecyl-1,1,3-tris(2'-methyl-5'-t-butyl-4'-oxyphenyl)butanediphosphite, tetra(C12-15 mixed alkyl)-4,4'-isopropylidenediphenyldiphosphite and the like. Preferably, these phosphite antioxidants caneach be used in an amount of 0.01 to 10 wt % based on the resin.

In the thermal stabilization method for a resin regarding the presentinvention, the production of the resin and the use of other additivescan be conducted in a similar manner to the above-describedflame-retarding method of the resin but are not limited.

The resins to which the thermal stabilization method of the resinregarding the present invention can be applied are preferablythermoplastic resins, thermoplastic elastomers and synthetic waxes. Morepreferable is at least one selected from the group consisting ofpolyphenyleneether resins, polyacrylic resins, polystyrene resins,polyamide resins, polyolefin resins, olefin base thermoplasticelastomers and hydrocarbon base synthetic waxes. The preferablepolyolefin resin is at least one selected from the group consisting ofpolyethylene resins, polypropylene resins and ethylene-propylenecopolymers.

D. According to a compatibilizing method of resins regarding the presentinvention, at least one of the modified resin described in theabove-mentioned paragraph (a) and the epoxy-modified resin described inthe above-mentioned paragraph (i) is compatibilized with two other kindsof resins. As a result, the compatibility and dispersibility of thedifferent kinds of resins can be remarkably improved, and a new materialcan be provided in which physical properties are improved; at the timeof high-temperature working, the heat deterioration, coloring and colorchange of the resin can be inhibited, and the resulting material isexcellent in high-temperature stability and non-volatility, can inhibitthe generation of sublimation and bleeding, and is easy to handle andmanufacture; even the compatibility and dispersibility between theresins having largely different solubility parameters can be improved,and therefore many kinds of resins are selectable and applicable, sothat various kinds of new materials can be provided; since the molecularweight reduction and the quality change of the new material scarcelytake place because of neither the decomposition nor gelation of theoriginal resins, the characteristics of the resins can easily bemaintained, so that the excellent new materials can easily be obtained;and the thermal stability of the material obtained by thecompatibilization can also be improved. In consequence, the excellentmodification method of a resin can be provided.

In the compatibilizing method of resins regarding the present invention,at least one of the aforesaid modified resin and epoxy-modified resincan be used in a suitable amount, and the modified resin may occupy atotal portion or a partial portion of the corresponding resin. Usually,the modified resin is used in such an amount that the content of areaction residue of the above-mentioned norbornenyl group-containingcompound in the corresponding resin is in the range of from 0.1 to 30 wt%, but the amount of the modified resin can be suitably selected inaccordance with the use purpose. If the content of the reaction residueis less than 0.1 wt %, a sufficient compatibilization effect canscarcely be obtained, and on the other hand, if it is more than 30 wt %,the compatibilization effect is not particularly improved any more,which is not preferable from an economical viewpoint. The epoxy-modifiedresin is used in such an amount that the content of a reaction residueof the above-mentioned epoxide in the corresponding resin is in therange of from 0.1 to 40 wt %, preferably from 0.5 to 30 wt %, but theamount of the epoxy-modified resin can be suitably selected inaccordance with the use purpose. If the content of the reaction residueis less than 0.1 wt %, a sufficient compatibilization effect canscarcely be obtained, and on the other hand, if it is more than 40 wt %,the compatibilization effect is not particularly improved any more, andthe characteristics of the resin easily deteriorate unpreferably.

As the compatibilizing methods of resins regarding the presentinvention, useful are a method which comprises incorporating at leastone selected from the group consisting of the modified resin and theepoxy-modified resin into one or more other kinds of resins, and anothermethod which comprises incorporating two or more different kinds of themodified resin and the epoxy-modified resin thereinto. These exemplifiedmethods are not restrictive.

From the modified resins regarding the present invention, the materialshaving the various functional groups can be provided, and modificationcan further be enhanced by the use of these materials. Like theaforesaid modified resins, these materials can be used in thecompatibilizing method regarding the present invention. The modifiedresins obtained by the use of the norbornenyl group-containing compoundrepresented by the formula (2) are preferred, because they have anactive amino group which is excellent in reactivity and can be furthermodified by a modification reaction with not only the above-mentionedepoxide but also a carboxylic acid (anhydride) of a maleicanhydride-modified polypropylene resin or the like, an isocyanate of apolyurethane resin or the like, an oxazoline of astyrene-2-vinyl-2-oxazoline copolymer or the like and an aldehyde ofterephthalcarbaldehyde or the like. These materials are useful in thecompatibilizing method regarding the present invention, similarly to theabove-mentioned modified resins.

Resins to which the compatibilizing method of resins regarding thepresent invention can be applied are substantially the same as theresins applicable to the manufacturing method of the modified resins,but preferable examples of the resins include polyolefin resins,polyphenyleneether resins, saturated polyester resins, polyamide resins,polycarbonate resins, polystyrene resins and thermoplastic elastomers.Typical examples of the two or more different kinds of resins include,but are not limited to, different kinds of binary and multiple resins ofpolyolefin resins and polyamide resins, polyphenyleneether resins,polystyrene resins, polyimide resins and saturated polyester resins,different kinds of binary and multiple resins of polyphenyleneetherresins and polyamide resins, polyimide resins, polyaramid resins andsaturated polyester resins, different kinds of binary and multipleresins of elastomers and polyolefin resins, polyamide resins,polyphenyleneether resins, polystyrene resins, polyimide resins andsaturated polyester resins, and different kinds of binary and multipleresins of saturated polyester resins and other resins.

As the useful compatibilizing methods of resins regarding the presentinvention, there are a method which comprises simultaneously carryingout the manufacturing process of the aforesaid modified resin orepoxy-modified resin and the compatibilizing process of different kindsof resins, and a method which comprises first obtaining the aforesaidmodified resin or epoxy-modified resin, and then compatibilizingdifferent kinds of resins by the use of the obtained modified resin orepoxy-modified resin. A suitable method can be selected from thesemethods in compliance with a use purpose, but these methods are notrestrictive.

No particular restriction is put on a method for preparing the materialand usually, there can be applied a solution method, a latex method anda melting method which can be used in the compatibilizing method of theresins. For example, the pellets or powder of the resin is first mixedat ordinary temperature, and then molten, mixed and molded by the use ofa machine for kneading such as a single screw extruder, a twin-screwextruder, heating rolls, a Bumbury's mixer and a kneader. This method isnot restrictive.

In the compatibilizing method of resins regarding the present invention,some additives can be used in the same amounts as described above inconnection of the above-mentioned method, and examples of the additivesinclude phenolic antioxidants, amine-base antioxidants,sulfur-containing antioxidants, phosphite-containing antioxidants, lightstabilizers, nucleating agents and other additives. These additives canbe chosen as needed depending on an application purpose.

E. In a surface modification method of resins regarding the presentinvention, at least one resin of the modified resins described in theabove-mentioned paragraphs (b) to (d) and the epoxy-modified resindescribed in the above-mentioned paragraph (i) is used. As a result,wettability, adhesive properties, coating properties, dyeability,water/oil repellency, solvent resistance and the like of the resin canbe improved; since the high-molecular weight resin itself is modifiedand denatured instead of adding a low-molecular weight additive, themodified resin is excellent in high-temperature stability andnon-volatility, and the diminution of the effect due to the loss of amodifier with time or by heat or the like does not take place; theseparation and loss of the modifier by poor compatibility with the resinscarcely occur; and the wettability on the surface of the resin can beselected in compliance with a use purpose. In consequence, an excellentsurface modification method of a resin can be provided.

The surface modification method of a resin regarding the presentinvention is particularly useful for polyolefin resins such aspolypropylene resins in which surface properties such as adhesiveproperties, coating properties and dyeability are noticeably limited.These resins have excellent physical properties and characteristics, buttheir applications are severely limited, because of having these seriousfaults. By virtue of this surface modification method, however, thesefaults can be eliminated, so that the development of these resins iswidely possible in many applications.

In addition, polypropylene fibers have excellent features such as beinglight, strong, warm and easily dryable, but on the other hand, they havea serious defect of the surface properties that dyeability is noticeablypoor. For this reason, the applications of the polypropylene fibers arenoticeably limited.

As techniques for improving the dyeability, many suggestions have beenmade which comprise, for example, adding a modifier or utilizing amaleic acid-modified polypropylene fiber. However, these suggestedmethods are some disadvantages. For example, the sufficient dyeabilityis not obtained; the dispersion and compatibility of the modifier areinsufficient; heat resistance noticeably deteriorates; and weatheringresistance is poor.

According to the surface modification method of a resin regarding thepresent invention, the functional group for remarkably improving thedyeability can be bonded and introduced to the resin as much asrequired, and thus most satisfactorily improving dyeability can beimparted by the modification. For example, the dyeability is excellent;any anxiety about dispersion and compatibility is not present; heatresistance and weathering resistance are excellent; and quality changeand heat deterioration of the obtained resin by the molecular weightreduction and the like can be sufficiently inhibited.

The manufacture and dyeing method of the modified fibers can be carriedout by the use of a known spinning procedure, a known dye, known dyeingconditions and known soaping procedure and the like. Since anaminotriazinyl group is introduced and bonded to the thus modifiedfiber, a dye such as an acid dyeing is advantageous, which is notrestrictive.

According to the surface modification method of a resin regarding thepresent invention, on the surface of the resin provided from themodified resin obtained by the use of the norbornenyl group-containingcompound represented by the formula (2), an active amino group having anexcellent activity is present in large quantities. Therefore, this resinsurface may be treated with an aldehyde, an epoxide, a carboxylic acid(anhydride), an isocyanate, an oxazoline, silanes such as a chlorosilaneand an alkoxysilane, a silazane or a silane such as a specific silylagent, silane coupling agents such as a vinylsilane, an epoxysilane anda fluorine-containing silane to further modify the surface. This methodis also very useful.

According to the present invention, there can be provided a coatingresin composition having good coating properties which comprises usingat least one resin selected from the group consisting of the modifiedresins described in the above-mentioned paragraphs (b) to (d) and theepoxy-modified resin described in the above-mentioned paragraph (i).Since the coating resin composition contains a segment having a goodcompatibility with resins, the composition is excellent in adhesiveproperties to a material, and it is also excellent in solventresistance, water resistance and coating properties. Furthermore,according to the present invention, there can be provided an adhesiveresin composition having good adhesive properties which comprises usingat least one resin selected from the group consisting of the modifiedresins described in the above-mentioned paragraphs (b) to (d) and theepoxy-modified resin described in the above-mentioned paragraph (i).Since the adhesive resin composition contains a segment having a goodcompatibility with a resin and a segment having good adhesive propertiesto another base material, the composition is excellent in adhesiveproperties to the material. The composition can also be used togetherwith various materials to provide a composite material.

In the surface modification method of a resin regarding the presentinvention, with regard to the amount of the modified resin or theepoxy-modified resin to be used, this modified resin may occupy a totalportion or a partial portion of the resin. The modified resin and theepoxy-modified resin can be effectively used singly or in a combination.The employment of the epoxy-modified resin is particularly preferable,because the adhesive properties to a desired material can be suitablyselected in compliance with a use purpose to accomplish the excellentsurface modification. For example, for a resin such as a polyolefinresin or a polystyrene resin, the resin is usually used together with arubber such as an olefin base thermoplastic elastomer so as to improvephysical properties. However, when the modification of surfaceproperties such as wettability, adhesive properties and coatingproperties is intended, both or either of the modified resin and themodified rubber can be used in such an amount as to occupy a totalportion or a partial portion of the resin, thereby modifying the surfacecharacteristics. These conditions can be suitably selected in compliancewith a use purpose.

The modified resin is used in such an amount that the content of areaction residue of the above-mentioned norbornenyl group-containingcompound in the corresponding resin is in the range of from 0.1 to 30 wt%, but the amount of the modified resin can be suitably selected inaccordance with the use purpose. If the content of the reaction residueis less than 0.1 wt %, a sufficient surface modification effect canscarcely be obtained, and on the other hand, if it is more than 30 wt %,the modification effect is not particularly improved any more and thecharacteristics of the resin deteriorate, which is not preferable froman economical viewpoint.

Furthermore, the epoxy-modified resin is used in such an amount that thecontent of a reaction residue of the above-mentioned epoxide in thecorresponding resin is in the range of from 0.1 to 30 wt %, but theamount of the modified resin can be suitably selected in accordance withthe use purpose. If the content of the reaction residue is less than 0.1wt %, a sufficient surface modification effect can scarcely be obtained,and on the other hand, if it is more than 30 wt %, the characteristicsof the resin easily deteriorate, which is not preferable.

In the surface modification method of a resin regarding the presentinvention, the production of the resin and the use of other additivescan be conducted in a similar manner to the above-describedflame-retarding method of a resin but are not limited.

In the above-mentioned coating resin composition, the amount of themodified resin or the epoxy-modified resin may occupy a total portion ora partial portion of the resin composition. The modified resin and theepoxy-modified resin can be effectively used singly or in a combination,but the employment of the epoxy-modified resin is particularlypreferable, because the epoxy-modified resin is very excellent inadhesive properties to the various resins, solvent resistance, waterresistance and the like. Moreover, the epoxy-modified resin obtained byusing bisphenol A, bisphenol F or a compound having a naphthaleneskeleton as the epoxide is preferable.

In the above-mentioned adhesive resin composition, the amount of themodified resin or the epoxy-modified resin may occupy a total portion ora partial portion of the resin composition. The modified resin and theepoxy-modified resin can be effectively used singly or in a combination,but the employment of the epoxy-modified resin is particularlypreferable, because the epoxy-modified resin is very excellent inadhesive properties to the various resins. Moreover, the epoxy-modifiedresin obtained by using bisphenol A, bisphenol F or a compound having anaphthalene skeleton as the epoxide is particularly preferable, becauseof being excellent in adhesive properties to various materials.

The adhesive resin composition may be in either state of a solvent type,a non-solvent type or a solid melting use type such as a hot-melt typeadhesive and a room temperature fluid type such as a tackifyingadhesive, and the desired type of the adhesive resin composition can besuitably selected in compliance with a use purpose.

A manufacturing method of the aforesaid modified resin and the likeregarding the present invention as well as its utilization lead to thefollowing functional effects.

The method for preparing the aforesaid modified resin regarding thepresent invention can be accomplished by reacting the above-mentionednorbornenyl group-containing compound with a resin under specificconditions. According to this preparation method, the modification canbe done without impairing the molecular weight, physical properties andthe like of the resin, and there can be bonded and introduced, to theresin, a functional group effective to improve the properties such asflame retardancy, thermal stability, heat resistance, compatibility,surface properties such as wettability, adhesive properties, coatingproperties and dyeability, moldability, electrical properties, gloss andthe like. Furthermore, a method for preparing the aforesaidepoxy-modified resin of the present invention can be accomplished byreacting the aforesaid specific modified resin and an epoxide underspecific conditions. This preparation method can be easily carried out,and the modification can be sufficiently done to remarkably improvesurface properties such as wettability, coating properties, adhesiveproperties and dyeability, moldability, electrical properties and thelike of the resin. In addition, the aforesaid modified resin andepoxy-modified resin can be utilized to further improve thecompatibility and dispersibility between different kinds of resins. Forthese advantages, the methods for preparing the aforesaid modified resinand epoxy-modified resin can be widely developed in many applications,and hence it is fair to say that these methods can be industrially veryuseful.

According to the flame-retarding method of a resin regarding the presentinvention, the flame retardancy of the resin can be remarkably improvedby using the aforesaid modified resin or epoxy-modified resin obtainedby the use of the norbornenyl group-containing compound represented bythe formula (2), its condensate or its etherified condensate. Incontrast to a method which comprises adding a flame-retardant such asmelamine, the method of the present invention can inhibit the generationof sublimation, bleeding and the like, and since a flameretardancy-imparting component is bonded and introduced to the resin,the loss of the component with time and a dispersion failure such asbleeding scarcely occur. Therefore, the effect of the component can bemaintained for a long time, whereby the flame retardancy of the obtainedresin can be remarkably improved. The characteristics and physicalproperties of the original resin are not impaired, and the charformability and the like of the obtained resin are extremely good, sothat the sagging or dripping of oil droplets or a melt can be remarkablydecreased. In addition, an extremely noxious gas is not given off duringburning. It is apparent from the foregoing that the flame retardancyimprovement effect of the obtained resin is excellent. When theaforesaid modified resin is used together with phosphoruses, anisocyanuric acid, a cyanuric acid or an amino group-containing compound,a synergistic effect can be obtained to further improve the flameretardancy. For these advantages, the obtained resins can be widelydeveloped in many applications, and the present invention can beconsidered to be industrially very useful.

The thermal stabilization method of a resin regarding the presentinvention can be accomplished by the use of the aforesaid modified resinor epoxy-modified resin which can be obtained by employing thenorbornenyl group-containing compound of the formula (2), its condensateor its etherified condensate. In the thus thermally stabilized resin,ultraviolet light resistance, heat stability, heat resistance and thelike can be remarkably improved, and even when molding is made at a hightemperature, heat deterioration, coloring and color change can beinhibited, which means that the stabilized resin is improved in heatstability and heat resistance. Even when used at a relatively hightemperature for a long period of time, the resin scarcely deteriorates,so that its physical properties can be maintained very satisfactorily.Since the thermal stability-imparting component is bonded and introducedto the resin, the loss of the component with time and a dispersionfailure such as bleeding scarcely occur, so that the effect of thecomponent can be maintained for a long time and thus a stability effectto heat, light and the like is also sufficient and it can be exerted fora long time without inducing any secondary troubles. In addition, thestabilized resin can sufficiently protected from decomposition ordeterioration by heavy metal ions such as copper ions, and since thermalstability and heat resistance can be remarkably improved, thehigh-temperature molding and working of the resin can be very easilyaccomplished. Thus, the resin thermally stabilized by the method of thepresent invention is extremely excellent in thermal stabilizationimprovement effect, and so the method permits the offer of new materialshaving such excellent characteristics as described above. For theseadvantages, the thermally stabilized resins can be widely developed inmany applications, and the method of the present invention can beconsidered to be industrially very useful.

The compatibilizing method of resins regarding the present invention canbe accomplished by using the aforesaid modified resin or epoxy-modifiedresin together with two or more different kinds of resins. In the thuscompatibilized resins, the compatibility and dispersion of the differentkinds of resins can be remarkably improved, and this method permits theoffer of new materials to which new characteristics such as impactresistance, stiffness, flame retardancy, heat resistance, chemicalresistance, barrier properties, pearl gloss, moldability/workability,adhesive properties and coating properties can be imparted. Furthermore,in the compatibilized resins, coloring and color change athigh-temperature working can be inhibited, and these resins are alsoexcellent in high-temperature stability and non-volatility. Thecompatibilized resins can inhibit the generation of sublimation,bleeding and the like, and they are also excellent in adhesiveproperties, electrical properties and the like and their handling andmanufacturing are easy. According to the present invention, even thecompatibility and dispersibility between the resins having largelydifferent solubility parameters can be improved, and therefore manykinds of resins are selectable and applicable. In the compatibilizedresins, their molecular weight reduction, quality change and the like,which are caused by the decomposition or the like of the originalresins, scarcely occur, so that the characteristics of thecompatibilized resins can be easily maintained. The aforesaid modifiedresin or epoxy-modified resin can also be obtained from the differentkinds of resins themselves to be compatibilized, and in this case, athird component such as a low-molecular weight compound for thecompatibilization is not required, so that excellent new materials canbe provided. In addition, this modified resin or epoxy-modified resinfunctions to improve thermal stability, water resistance and chemicalresistance in the compatibilized resins. For these advantages, thecompatibilized resins can be widely developed in many applications, andthe method of the present invention can be considered to be industriallyvery useful.

The surface modification method of a resin regarding the presentinvention can be accomplished by using the aforesaid modified resin orepoxy-modified resin. In the thus surface modification resin, surfaceproperties such as wettability, adhesive properties, coating properties,dyeability and water/oil repellency can be remarkably improved, andsince any third component such as a surface modifier is not required,the decrease of the effect due to the loss of the surfacemodification-imparting component does not occurs any more, so that thephysical properties of the resin do not lower, either. It is notnecessary to carry out the surface modification after molding or thelike, and therefore the good and uniform surface modification can bedone for molded articles having various shapes. In particular, accordingto another excellent feature of the present invention, the functionalgroup of the aforesaid modified resin or epoxy-modified resin can bebonded and introduced to polyolefin resins and the like which canscarcely accept surface properties such as adhesive properties, coatingproperties and dyeability, whereby the surface properties of these kindsof resins and their fibers can be remarkably improved.

Moreover, the present invention can provide a coating resin compositionand a adhesive resin composition obtained by the use of the aforesaidmodified resin or epoxy-modified resin. The coating resin composition isexcellent in adhesive properties to a resin, solvent resistance, waterresistance and the like, and the adhesive resin composition contains asegment having a good compatibility with a resin and a segment havinggood adhesive properties to another base material, and hence theadhesive resin composition is excellent in adhesive properties tovarious materials. Thus, according to this invention, new materials canbe provided. For these advantages, the above-mentioned compositions canbe widely developed in many applications, and the method of the presentinvention can be considered to be industrially very useful.

Next, the present invention will be described in more detail withreference to reference examples and examples. However, the scope of thepresent invention should not be limited by these reference examples andexamples at all.

REFERENCE EXAMPLE 1

Preparation of norbornenecarboguanamine-formaldehyde condensate:

243.2 g (3.0 mols) of a 37% formalin was added to 203.0 g (1 mol) of2-(4,6-diamino-1,3,5-triazin-2-yl)bicyclo 2.2.1!hept-5-ene (hereinafterabbreviated to "norbornenecarboguanamine"), and the mixture was thenadjusted to pH 10.5 with a 20% aqueous potassium hydroxide solutionunder mixing and stirring. Next, this mixture was heated at atemperature of 70° C. for 1 hour under stirring. After the completion ofthe heating, a 20% aqueous nitric acid solution was added to thisreaction mixture to adjust the same to pH 2.0. Furthermore, thisreaction mixture was heated at a temperature of 70° C. under stirring toslowly become turbid, and this heating was continued for 3 hours tocarry out reaction. After the completion of the heating, this reactionmixture was adjusted to pH 8.0 with a 20% aqueous potassium hydroxidesolution, and the resulting precipitate was then collected byfiltration. The collected precipitate was sufficiently washed withdistilled water, and then dried under reduced pressure to obtain a whitesolid. As a result of the analysis of the solid, it was apparent thatthe solid was a condensate having an average addition condensationdegree of 3.8.

REFERENCE EXAMPLE 2

Preparation of norbornenecarboguariamine-formaldehyde condensate:

243.2 g (3.0 mols) of a 37% formalin was added to 203.0 g (1 mol) ofnorbornenecarboguanalmine, and the mixture was then adjusted to pH 10.5with a 20% aqueous potassium hydroxide solution under mixing andstirring. Next, this mixture was heated at a temperature of 70° C. for30 minutes under stirring. After the completion of the heating, a 20%aqueous nitric acid solution was added to this reaction mixture toadjust the same to pH 4.0. Furthermore, this reaction mixture was heatedat a temperature of 60° C. under stirring to slowly become turbid, andthis heating was continued for 1 hour to carry out reaction. After thecompletion of the heating, this reaction mixture was adjusted to pH 7.0with a 20% aqueous potassium hydroxide solution. Next, 200 g of benzenewas added to the reaction mixture, followed by heating to removebenzene. Afterward, the resulting precipitate was then collected byfiltration. The collected precipitate was sufficiently washed withdistilled water, and then dried under reduced pressure to obtain a whitesolid. As a result of the analysis of the solid, it was apparent thatthe solid was a condensate having an average addition condensationdegree of 1.6.

REFERENCE EXAMPLE 3

Preparation of etherified condensate of norbornenecarboguanamine:

131.3 g (3.5 mols) of paraformaldehyde (80%) and 500 ml of n-butanolwere added to 203.0 g (1 mol) of norbornenecarboguanamine, and themixture was then adjusted to pH 11.0 with a 20% aqueous potassiumhydroxide solution under mixing and stirring. Afterward, this mixturewas heated at a temperature of 60° C. for 30 minutes under stirring, anda 20% aqueous nitric acid solution was then added to the mixture toadjust the same to pH 3.0. Furthermore, the resulting reaction mixturewas heated for 3 hours under stirring, while reflux dehydration wascarried out under reflux temperature conditions. After the completion ofthe heating, a 20% aqueous potassium hydroxide was added to thisreaction mixture to adjust the same to pH 8.0, and the resultingprecipitate was then removed by filtration. Next, the solvent wasremoved from the solution to obtain a resinous product. As a result ofanalysis, it was apparent that the product was an etherified condensatecontaining a butyl ether group and having an average additioncondensation degree of 2.3.

REFERENCE EXAMPLE 4

Preparation of epoxidized polyphenyleneether resin:

In a 2-liter autoclave equipped with a stirrer and an inlet were placed20 g of a polyphenyleneether resin (number-average molecularweight=21,000) and 1 liter of epichlorohydrin, and the autoclave wasthen purged with nitrogen. Afterward, the mixture was slowly heated upto 100° C., and the resin was dissolved by stirring, while thetemperature in the autoclave was maintained at 100° C. Next, 5 cc of a10% aqueous sodium hydroxide solution was added to the solution, andreaction was then carried out at an inside temperature of 100° C. for 5hours. After the completion of the reaction, remaining epichlorohydrinwas distilled off under reduced pressure, and chloroform was added tothe resulting solid to dissolve it. From the solution, insolubles wereremoved by filtration, and a methanol-water mixed solvent was then addedto the solution. Next, the deposited precipitate was collected byfiltration, sufficiently washed with the above-mentioned mixed solvent,and then dried under reduced pressure to obtain an epoxidizedpolyphenyleneether resin. As a result of analysis of the resin, it wasapparent that the resin had an epoxy equivalent of 24,000.

EXAMPLE 1

Preparation of modified polypropylene resin:

100 parts by weight of a polypropylene resin (trade name Mitsui NOBLENJS-G, made by Mitsui Toatsu Chemicals Inc.) was sufficiently mixed with10 parts by weight of norbornenecarboguanamine and 0.1 part by weight ofdilauryl thiodipropionate by a Henschel mixer. Afterward, the mixturewas fed to a twin-screw extruder equipped with a 20-mm vent sealed withnitrogen, and kneading and reaction were then carried out under suchconditions that the mixture was allowed to reside at 260° C. for 10minutes, followed by pelletizing.

The resulting pellets were dissolved in hot xylol, and the solution wasthen filtered through a membrane filter (pore diameter=1.0 μm). To thefiltrate, methyl cellosolve was poured, and the deposited precipitatewas collected by filtration, sufficiently washed with methyl cellosolve,and then dried under reduced pressure to obtain a white solid. As aresult of the analysis of this solid, it was apparent that the solid wasa modified polypropylene resin to which 4.9 wt % of a4,6-diamino-1,3,5-triazine skeleton was bonded. The results of theelemental analysis and infrared absorption spectrum analysis of thissolid were as follows.

    ______________________________________                                        Elemental analysis                                                                   C            H       N                                                 ______________________________________                                        Found:   83.1%          13.8%   3.1%                                          ______________________________________                                    

Infrared absorption spectrum analysis

NH₂ -based absorption 3320, 3150 cm⁻¹

C═N-based absorption 1630, 1550 cm⁻¹

Triazine ring-based absorption 815 cm⁻¹

EXAMPLE 2

Preparation of modified polypropylene resin:

Kneading and reaction were carried out by the same procedure as inExample 1 except that 10 parts by weight of norbornenecarboguanamine inExample 1 was replaced with 25 parts by weight of the same compound,followed by pelletizing.

The pellets were treated with a solvent in the same manner as inExample 1. The resulting solid was dried under reduced pressure, andthen subjected to analysis. As a result, it was apparent that the solidwas a modified polypropylene resin to which 10.9 wt % of a4,6-diamino-1,3,5-triazine skeleton was bonded. The results of theelemental analysis of this solid were as follows.

Furthermore, the measured MI value of the pellets of this solid was 1.8.On the other hand, as a comparative example, a solid was obtained bysimilarly kneading the above-mentioned polypropylene resin alone, andits MI value was 2.3. The preparation method of the present inventionwas so excellent that the molecular weight reduction, color change andthe like of the resin were scarcely brought about.

    ______________________________________                                        Elemental analysis                                                                   C            H       N                                                 ______________________________________                                        Found:   80.1%          13.0%   6.9%                                          ______________________________________                                    

EXAMPLE 3

Preparation of modified polypropylene resin:

Kneading and reaction were carried out by the same procedure as inExample 1 except that a polypropylene resin (trade name Mitsui NOBLENJS-G, made by Mitsui Toatsu Chemicals Inc.) in Example 1 was replacedwith a polypropylene resin having a low polymerization degree of MIvalue=100, followed by pelletizing.

The pellets were treated with a solvent in the same manner as inExample 1. The resulting solid was dried under reduced pressure, andthen subjected to analysis. As a result, it was apparent that the solidwas a modified polypropylene resin to which 4.9 wt % of a4,6-diamino-1,3,5-triazine skeleton was bonded. The results of theelemental analysis of this solid were as follows.

    ______________________________________                                        Elemental analysis                                                                   C            H       N                                                 ______________________________________                                        Found:   83.2%          13.7%   3.1%                                          ______________________________________                                    

COMPARATIVE EXAMPLE 1

Modification test of polypropylene resin:

Kneading and reaction were carried out by the same procedure as inExample 1 except that 10 parts by weight of norbornenecarboguanamine inExample 1 was replaced with 10 parts by weight of2-(4,6-diamino-1,3,5-triazin-2-yl)bicyclo 2.2.1!heptane, followed bypelletizing.

The pellets were treated with a solvent in the same manner as inExample 1. The resulting solid was dried under reduced pressure, andafterward, for the solid, elemental analysis and infrared absorptionspectrum analysis were made. As a result, it was apparent that thepresence and bond of a 4,6-diamino-1,3,5-triazine skeleton were notconfirmed as in the raw material polypropylene resin, which meant thatthe raw material polypropylene resin was not modified. The results ofthe elemental analysis of this solid were as follows.

    ______________________________________                                        Elemental analysis                                                                   C            H       N                                                 ______________________________________                                        Found:   85.6%          14.4%   0.0%                                          ______________________________________                                    

COMPARATIVE EXAMPLE 2

Modification test of polypropylene resin:

100 parts by weight of a polypropylene resin (trade name Mitsui NOBLENJS-G, made by Mitsui Toatsu Chemicals Inc.) was sufficiently mixed with10 parts by weight of 5-norbornene-2,3-dicarboxylic anhydride and 0.1part by weight of dilauryl thiodipropionate by a Henschel mixer.Afterward, the mixture was fed to a twin-screw extruder equipped with a20-mm vent sealed with nitrogen, and kneading and reaction were thencarried out under such conditions that the mixture was allowed to resideat 240° C. for 10 minutes, followed by pelletizing.

The resulting pellets were dissolved in hot xylol, and the solution wasthen filtered through a membrane filter (pore diameter=1.0 μm). To thefiltrate, methanol was poured, and the deposited precipitate wascollected by filtration, sufficiently washed wish methanol, and thendried under reduced pressure to obtain a white solid. As a result of theinfrared absorption spectrum analysis of this solid, it was apparentthat neither carboxylic acid-based absorption nor carboxylicanhydride-based absorption (at 1710, 1770, 1785, 1860 cm⁻¹ and the like)were confirmed, which meant that the polypropylene resin was notmodified at all.

Furthermore, kneading, reaction, treatment and analysis were carried outby the same procedure as described above except that a kneadingtemperature of 240° C. was replaced with a kneading temperature of 260°C. or 280° C. As a result, it was apparent that even under thesekneading conditions, the polypropylene resin was not modified at all.

COMPARATIVE EXAMPLE 3

Modification test of polypropylene resin:

Kneading and reaction were carried out by the same procedure as inComparative Example 2 except that 10 parts by weight of5-norbornene-2,3-dicarboxylic anhydride in Comparative Example 2 wasreplaced with 10 parts by weight of maleic anhydride, followed bypelletizing.

The pellets were treated in the same manner as in Comparative Example 2to obtain a white solid. For this solid, infrared absorption spectrumanalysis was made. As a result, it was apparent that neither carboxylicacid-based absorption nor carboxylic anhydride-based absorption (at1710, 1770, 1785, 1860 cm⁻¹ and the like) were confirmed, which meantthat the polypropylene resin was not modified at all.

EXAMPLE 4

Preparation of modified polyethylene resin:

Kneading and reaction were carried out by the same procedure as inExample 1 except that a polypropylene resin (trade name Mitsui NOBLENJS-G, made by Mitsui Toatsu Chemicals Inc.) in Example 2 was replacedwith a polyethylene resin (trade name HIZEX 6200BP, made by MitsuiPetrochemical Industries, Ltd.), followed by pelletizing.

The pellets were treated with a solvent in the same manner as inExample 1. The resulting solid was dried under reduced pressure, andafterward, for the solid, elemental analysis and infrared absorptionspectrum analysis were made. As a result, it was apparent that the solidwas a modified polyethylene resin to which 11.3 wt % of a4,6-diamino-1,3,5-triazine skeleton was bonded. The results of theelemental analysis of this solid were as follows.

    ______________________________________                                        Elemental analysis                                                                   C            H       N                                                 ______________________________________                                        Found:   79.8%          13.0%   7.2%                                          ______________________________________                                    

EXAMPLE 5

Preparation of modified polyphenyleneether resin:

100 parts by weight of poly(2,6-dimethyl-1,4-phenyleneether) having anintrinsic viscosity η! of 0.42 was sufficiently mixed with 10 parts byweight of norbornenecarboguanamine and 0.1 part by weight of dilaurylthiodipropionate by a Henschel mixer. Afterward, the mixture was fed toa twin-screw extruder equipped with a 20-mm vent sealed with nitrogen,and kneading and reaction were then carried out under such conditionsthat the mixture was allowed to reside at 310° C. for 10 minutes,followed by pelletizing.

The resulting pellets were dissolved in chloroform, and the solution wasthen filtered through a membrane filter (pore diameter=1.0 μm). To thefiltrate, methyl cellosolve was poured, and the deposited precipitatewas collected by filtration, sufficiently washed with methyl cellosolve,and then dried under reduced pressure to obtain a yellow solid. As aresult of the analysis of this solid, it was apparent that the solid wasa modified polyphenyleneether resin (a nitrogen content in theunmodified resin was 0.1 wt %) to which 4.9 wt % of a4,6-diamino-1,3,5-triazine skeleton was bonded. The results of theelemental analysis of this solid were as follows.

Furthermore, the molecular weight of the pellets was measured by GPC,and as a result, it was apparent that the molecular weight was about thesame as that of the raw material polyphenyleneether resin before theabove-mentioned kneading and reaction. Thus, the preparation method ofthe present invention was so excellent that the molecular weight change,color change and the like of the resin were scarcely brought about.

    ______________________________________                                        Elemental analysis                                                                   C            H       N                                                 ______________________________________                                        Found:   77.8%          6.6%    3.2%                                          ______________________________________                                    

EXAMPLE 6

Preparation of modified polystylene resin:

100 parts by weight of a polystylene resin (trade name TOPOLEX 570-2,made by Mitsui Toatsu Chemicals, Inc.) was sufficiently mixed with 5parts by weight of norbornenecarboguanamine and 0.1 part by weight oftris(2-methyl-4-hydroxy-5-t-butylphenyl)butane by a Henschel mixer.Afterward, the mixture was fed to a twin-screw extruder equipped with a20-mm vent sealed with nitrogen, and kneading and reaction were thencarried out under such conditions that the mixture was allowed to resideat 250° C. for 15 minutes, followed by pelletizing.

The resulting pellets were dissolved in chloroform, and the solution wasthen filtered through a membrane filter (pore diameter=1.0 μm). To thefiltrate, methyl cellosolve was poured, and the deposited precipitatewas collected by filtration, sufficiently washed with methyl cellosolve,and then dried under reduced pressure to obtain a white solid. As aresult of the analysis of this solid, it was apparent that the solid wasa modified polystylene resin to which 2.5 wt % of a4,6-diamino-1,3,5-triazine skeleton was bonded. The results of theelemental analysis and infrared absorption spectrum analysis of thissolid were as follows.

    ______________________________________                                        Elemental analysis                                                                   C            H       N                                                 ______________________________________                                        Found:   90.7%          7.7%    1.6%                                          ______________________________________                                    

Infrared absorption spectrum analysis

NH₂ -based absorption 3310, 3160 cm⁻¹

C═N-based absorption 1630, 1550 cm⁻¹

Triazine ring-based absorption 818 cm⁻¹

EXAMPLE 7

Preparation of modified saturated polyester resin:

100 parts by weight of a saturated polyester resin (trade name TeijinPBT Resin TRB-H, made by Teijin Limited) was sufficiently mixed with 10parts by weight of norbornenecarboguanamine and 0.1 part by weight oftris(2-methyl-4-hydroxy-5-t-butylphenyl)butane by a Henschel mixer.Afterward, the mixture was fed to a twin-screw extruder equipped with a20-mm vent sealed with nitrogen, and kneading and reaction were thencarried out under such conditions that the mixture was allowed to resideat 260° C. for 15 minutes, followed by pelletizing.

The resulting pellets were dissolved in dichloroethane, and the solutionwas then filtered through a membrane filter (pore diameter=1.0 μm). Tothe filtrate, methyl cellosolve was poured, and the depositedprecipitate was collected by filtration, sufficiently washed with methylcellosolve, and then dried under reduced pressure to obtain a whitesolid. As a result of the analysis of this solid, it was apparent thatthe solid was a modified saturated polyester resin to which 4.3 wt % ofa 4,6-diamino-1,3,5-triazine skeleton was bonded. The results of theelemental analysis and infrared absorption spectrum analysis of thissolid were as follows.

    ______________________________________                                        Elemental analysis                                                                   C            H       N                                                 ______________________________________                                        Found:   64.5%          5.5%    2.7%                                          ______________________________________                                    

Infrared absorption spectrum analysis

NH₂ -based absorption 3320, 3160 cm⁻¹

C═N-based absorption 1630, 1550 cm⁻¹

Triazine ring-based absorption 816 cm⁻¹

EXAMPLE 8

Preparation of modified polyamide resin:

100 parts by weight of a polyamide resin (trade name Toyobo Nylon T-802,made by Toyobo Co., Ltd.) was sufficiently mixed with 10 parts by weightof norbornenecarboguanamine by a Henschel mixer. Afterward, the mixturewas fed to a twin-screw extruder equipped with a 20-mm vent sealed withnitrogen, and kneading and reaction were then carried out under suchconditions that the mixture was allowed to reside at 250° C. for 15minutes, followed by pelletizing.

The resulting pellets were dissolved in m-cresol, and the solution wasthen filtered through a membrane filter (pore diameter=1.0 μm). To thefiltrate, methyl cellosolve was poured, and the deposited precipitatewas collected by filtration, sufficiently washed with methyl cellosolve,and then dried under reduced pressure to obtain a white solid. As aresult of the analysis of this solid, it was apparent that the solid wasa modified polyamide resin to which 4.8 wt % of a4,6-diamino-1,3,5-triazine skeleton was bonded. The results of theelemental analysis of this solid were as follows.

    ______________________________________                                        Elemental analysis                                                                   C            H       N                                                 ______________________________________                                        Found:   62.5%          9.5%    14.7%                                         ______________________________________                                    

EXAMPLE 9

Preparation of modified polymethacrylic resin:

100 parts by weight of a polymethacrylic resin (trade name Parapet HR,made by Kyowa Gas Chemical Indutries Inc.) was sufficiently mixed with10 parts by weight of norbornenecarboguanamine by a Henschel mixer.Afterward, the mixture was fed to a twin-screw extruder equipped with a20-mm vent sealed with nitrogen, and kneading and reaction were thencarried out under such conditions that the mixture was allowed to resideat 260° C. for 15 minutes, followed by pelletizing.

The resulting pellets were dissolved in methyl ethyl ketone, and thesolution was then filtered through a membrane filter (pore diameter=1.0μm). To the filtrate, methanol was poured, and the deposited precipitatewas collected by filtration, sufficiently washed with methanol, and thendried under reduced pressure to obtain a white solid. As a result of theanalysis of this solid, it was apparent that the solid was a modifiedpolymethacrylic resin to which 4.7 wt % of a 4,6-diamino-1,3,5-triazineskeleton was bonded. The results of the elemental analysis of this solidwere as follows.

    ______________________________________                                        Elemental analysis                                                                   C            H       N                                                 ______________________________________                                        Found:   55.4%          6.9%    3.0%                                          ______________________________________                                    

EXAMPLE 10

Preparation of modified EP rubber:

100 parts by weight of an EP rubber (trade name JSR EPOlP, made by JapanSynthetic Rubber Co., Ltd.) and 10 parts by weight ofnorbornenecarboguanamine were fed to a kneader equipped with a ventsealed with nitrogen, and kneading and reaction were carried out at 240°C. for 30 minutes and a kneaded material was then taken off.

The kneaded material was dissolved in hot xylol, and the solution wasthen filtered through a membrane filter (pore diameter=1.0 μm). To thefiltrate, methyl cellosolve was poured, and the resulting solid wascollected by filtration, sufficiently washed with methyl cellosolve, andthen dried under reduced pressure to obtain a white solid. As a resultof the analysis of this solid, it was apparent that the solid was amodified EP rubber to which 4.4 wt % of a 4,6-diamino-1,3,5-triazineskeleton was bonded. The results of the elemental analysis of this solidwere as follows.

    ______________________________________                                        Elemental analysis                                                                   C            H       N                                                 ______________________________________                                        Found:   83.4%          13.8%   2.8%                                          ______________________________________                                    

EXAMPLE 11

Preparation of modified PP wax:

100 parts by weight of a PP wax (trade name Mitsui HIWAX NP055, made byMitsui Petrochemical Industries, Ltd.) and 20 parts by weight ofnorbornenecarboguanamineformaldehyde condensate obtained by a method ofReference Example 1 were fed to a kneader equipped with a vent sealedwith nitrogen, and kneading and reaction were carried out at 260° C. for20 minutes and a kneaded material was then taken off.

The kneaded material was dissolved in hot xylol, and the solution wasthen filtered through a membrane filter (pore diameter=1.0 μm). To thefiltrate, methyl cellosolve was poured, and the resulting resinousmaterial was collected by separation. This treating operation wasrepeated twice, and the resinous material was then dried under reducedpressure to obtain a white solid. As a result of the analysis of thissolid, it was apparent that the solid was a modified PP wax to which 8.8wt % of a 4,6-diamino-1,3,5-triazine skeleton was bonded. The results ofthe elemental analysis of this solid were as follows.

    ______________________________________                                        Elemental analysis                                                                   C            H       N                                                 ______________________________________                                        Found:   81.3%          13.1%   5.6%                                          ______________________________________                                    

EXAMPLES 12 TO 16

Preparation of modified polypropylene resin:

Kneading and reaction were carried out by the same procedure as inExample 1 except that norbornenecarboguanamine in Example 1 was replacedwith each of norbornenyl group-containing compounds shown in Table 1,followed by pelletizing.

The resulting pellets were treated with a solvent in the same manner asin Example 1. The resulting solid was dried under reduced pressure, anda nitrogen content was then measured (elemental analysis). The resultsare shown in Table 1.

As shown in Table 1, when the reaction is carried out using thenorbornenyl group-containing compounds regarding the present invention,the excellent modified polypropylene resins can be prepared easily in ahigh yield.

                  TABLE 1                                                         ______________________________________                                                                     Elemental                                                   Norbornenyl Group-                                                                              Analysis                                         Example    Containing Compound                                                                             (N %)                                            ______________________________________                                        12         Etherified Condensate                                                                           2.4                                                         of Reference Example 3                                             13         2-(4,6-diamino-1,3,5-                                                                           2.7                                                         triazin-2-yl)-2-methyl-                                                       bicyclo 2.2.1!hept-5-ene                                           14         2- 4,6-bis(butoxymethyamino)-                                                                   1.6                                                         1,3,5-triazin-2-yl!-                                                          bicyclo 2.2.1!hept-5-ene                                           15         2- 4,6-bis(N,N-di-n-hexyl-                                                                      1.1                                                         amino)-1,3,5-triazin-2-yl!-                                                   bicyclo 2.2.1!hept-5-ene                                           16         2- 4,6-bis(2-hydroxyethyl-                                                                      2.1                                                         amino)-1,3,5-triazin-2-yl!-                                                   bicyclo 2.2.1!hept-5-ene                                           ______________________________________                                    

EXAMPLE 17

Preparation of modified polyethylene resin:

100 parts by weight of a polyethylene resin (trade name RextronJ79-4F25, made by Nippon Petrochemicals Co., Ltd.) was sufficientlymixed with 20 parts by weight of enecarboguanamine and 0.1 part byweight of dilauodipropionate by a Henschel mixer. Afterward, the was fedto a twin-screw extruder equipped with a 20-mm vent sealed withnitrogen, and kneading and reaction were then carried out under suchconditions that the mixture was allowed to reside at 280° C. for 10minutes, followed by pelletizing.

The resulting pellets were dissolved in hot xylol, and the solution wasthen filtered through a membrane filter (pore diameter=1.0 μm). To thefiltrate, methyl cellosolve was poured, and the deposited precipitatewas collected by filtration, sufficiently washed with methyl cellosolve,and then dried under reduced pressure to obtain a white solid. As aresult of the analysis of this solid, it was apparent that the solid wasa modified polyethylene resin to which 9.1 wt % of a4,6-diamino-1,3,5-triazine skeleton was bonded. The results of theelemental analysis of this solid were as follows.

    ______________________________________                                        Elemental analysis                                                                   C            H       N                                                 ______________________________________                                        Found:   80.9%          13.3%   5.8%                                          ______________________________________                                    

EXAMPLE 18

Preparation of modified polyethylene resin:

100 parts by weight of a polyethylene resin (trade name HIZEX 6200BP,made by Mitsui Petrochemical Industries, Ltd.) was sufficiently mixedwith 5 parts by weight of a reaction product of 5-norbornene-2-carbonylchloride and benzyl alcohol (1/1 molar ratio) and 0.1 part by weight ofdilauryl thiodipropionate by a Henschel mixer. Afterward, the mixturewas fed to a twin-screw extruder equipped with a 20-mm vent sealed withnitrogen, and kneading and reaction were then carried out under suchconditions that the mixture was allowed to reside at 260° C. for 10minutes, followed by pelletizing.

The resulting pellets were dissolved in hot xylol, and the solution wasthen filtered through a membrane filter (pore diameter=1.0 μm). To thefiltrate, m-cresol was poured, and the deposited precipitate wascollected by filtration, sufficiently washed with m-cresol, and thendried under reduced pressure to obtain a white solid. As a result of theinfrared absorption spectrum analysis of this solid, it was apparentthat the solid was a modified polyethylene resin having an ester bondand a phenyl skeleton.

EXAMPLE 19

Preparation of modified polyethylene resin:

100 parts by weight of a polyethylene resin (trade name HIZEX 6200BP,made by Mitsui Petrochemical Industries, Ltd.) was sufficiently mixedwith 5 parts by weight of a reaction product of 5-norbornene-2-carbonylchloride and 4,4'-diamino diphenylether (2/1 molar ratio) and 0.1 partby weight of dilauryl thiodipropionate by a Henschel mixer. Afterward,the mixture was fed to a twin-screw extruder equipped with a 20-mm ventsealed with nitrogen, and kneading and reaction were then carried outunder such conditions that the mixture was allowed to reside at 260° C.for 10 minutes, followed by pelletizing.

The resulting pellets were dissolved in hot xylol, and the solution wasthen filtered through a membrane filter (pore diameter=1.0 μm). To thefiltrate, m-cresol was poured, and the deposited precipitate wascollected by filtration, sufficiently washed with m-cresol, and thendried under reduced pressure to obtain a white solid. As a result of theinfrared absorption spectrum analysis of this solid, it was apparentthat the solid was a modified polyethylene resin having an amide bondand a phenyl skeleton.

EXAMPLE 20

Preparation of modified polyethylene resin:

Kneading and reaction were carried out by the same procedure as inExample 19 except that a reaction product of 5-norbornene-2-carbonylchloride and 4,4'-diamino diphenylether (2/1 molar ratio) was replacedwith a reaction product of 2-(bicyclo 2.2.1!hept-5-en-2-yl)-2-oxazolineand benzoic acid (1/1 molar ratio), followed by pelletizing.

The resulting pellets were treated with a solvent in the same manner asin Example 19. As a result of the infrared absorption spectrum analysisof the resulting solid, it was apparent that the solid was a modifiedpolyethylene resin having an amide bond, an ester bond and a phenylskeleton.

EXAMPLE 21

Preparation of modified paraffin wax:

100 parts by weight of a paraffin wax (trade name Paraffin Wax 155, madeby Nippon Seiro Co., Ltd.), 10 parts by weight ofnorbornenecarboguanamine and 0.1 part by weight of dilaurylthiodipropionate were fed to a 500-ml autoclave equipped with a vent, astirrer and a cooler. Next, the autoclave was purged with nitrogen, andreaction was then carried out at an inside temperature of 250° C. for 30minutes under stirring. After the completion of the reaction, theresulting resinous material was taken off as a reaction mixture.

This resinous material was dissolved in hot toluene, and the solutionwas then filtered through a membrane filter (pore diameter=1.0 μm). Tothe filtrate, methyl cellosolve was poured, and the resinous materialwas collected by separation. This treating operation was repeated twice,and the resinous material was then dried under reduced pressure toobtain a white solid. As a result of the analysis of this solid, it wasapparent that the solid was a modified paraffin wax to which 4.7 wt % ofa 4,6-diamino-1,3,5-triazine skeleton was bonded. The results of theelemental analysis of this solid were as follows.

    ______________________________________                                        Elemental analysis                                                                   C            H       N                                                 ______________________________________                                        Found:   83.2%          13.8%   3.0%                                          ______________________________________                                    

EXAMPLE 22

Preparation of EP-modified polypropylene resin:

100 parts by weight of the pellets of a modified polypropylene resinobtained by the procedure of Example 1 and 20 parts by weight of anepoxy resin (trade name Epicoat #1009, made by Yuka Shell Epoxy Co.,Ltd.) were sufficiently mixed by a mixer. Afterward, the mixture was fedto a twin-screw extruder equipped with a 20-mm vent sealed withnitrogen, and kneading and reaction were then carried out under suchconditions that the mixture was allowed to reside at 260° C. for 10minute, followed by pelletizing.

The resulting pellets were dissolved in hot xylol, and the solution wasthen filtered through a membrane filter (pore diameter=1.0 μm). To thefiltrate, methyl cellosolve was poured, and the deposited precipitatewas collected by filtration, sufficiently washed with methyl cellosolve,and then dried under reduced pressure to obtain a white solid. As aresult of the analysis of this solid, it was apparent that the solid wasan EP-modified polypropylene resin having a bisphenol A skeleton. Theresults of the elemental analysis and infrared absorption spectrumanalysis of this solid were as follows.

    ______________________________________                                        Elemental analysis                                                                   C            H       N                                                 ______________________________________                                        Found:   82.2%         13.0%    2.7%                                          ______________________________________                                    

Infrared absorption spectrum analysis

Phenyl ring-based absorption 1603, 1500 cm⁻¹

EXAMPLE 23

Preparation of EP-modified EP rubber:

100 parts by weight of a kneaded material of a modified EP rubberobtained by the procedure of Example 10 and 10 parts by weight of anepoxy resin (trade name Epicoat #1004 e by Yuka Shell Epoxy Co., Ltd.)were sufficiently mixed by a mixer. Afterward, the mixture was fed to akneader type extruder equipped with a 20-mm vent sealed with nitrogen,and kneading and reaction were then carried out under such conditionsthat the mixture was allowed to reside at 230° C. for 30 minutes. Next,the kneaded material was taken out.

This kneaded material was dissolved in hot xylol, and the solution wasthen filtered through a membrane filter (pore diameter=1.0 μm). To thefiltrate, methyl cellosolve was poured, and the resulting resinousmaterial was collected by separation. This treating operation wasrepeated twice, and the resinous material was then dried under reducedpressure to obtain a white solid. As a result of the analysis of thissolid, it was apparent that the solid was an EP-modified EP rubberhaving a bisphenol A skeleton. The results of the elemental analysis andinfrared absorption spectrum analysis of this solid were as follows.

    ______________________________________                                        Elemental analysis                                                                   C            H       N                                                 ______________________________________                                        Found:   82.8%          13.3%   2.6%                                          ______________________________________                                    

Infrared absorption spectrum analysis

Phenyl ring-based absorption 1603, 1501 cm⁻¹

EXAMPLE 24

Preparation of EP-modified PP wax:

100 parts by weight of a kneaded material of a modified PP wax obtainedby the procedure of Example 11 and 20 parts by weight of an epoxy resin(trade name Epicoat #1010, made by Yuka Shell Epoxy Co., Ltd.) weresufficiently mixed by a mixer. Afterward, the mixture was fed to akneader type extruder equipped with a vent sealed with nitrogen, andkneading and reaction were carried out at 230° C. for 20 minutes and thekneaded material was then taken out.

This kneaded material was dissolved in hot xylol, and the solution wasthen filtered through a membrane filter (pore diameter=1.0 μm). To thefiltrate, methyl ethyl ketone was poured, and the resulting resinousmaterial was collected by separation. This treating operation wasrepeated twice, and the resinous material was then dried under reducedpressure to obtain a white solid. As a result of the analysis of thissolid, it was apparent that the solid was an EP-modified PP wax having abisphenol A skeleton. The results of the elemental analysis and infraredabsorption spectrum analysis of this solid were as follows.

    ______________________________________                                        Elemental analysis                                                                   C            H       N                                                 ______________________________________                                        Found:   80.7%          12.5%   5.0%                                          ______________________________________                                    

Infrared absorption spectrum analysis

Phenyl ring-based absorption 1601, 1500 cm⁻¹

EXAMPLE 25

Preparation of EP-modified polyethylene resin:

100 parts by weight of the pellets of a modified polyethylene resinobtained by the procedure of Example 4 and 10 parts by weight ofp-benzylphenyl glycidyl ether were sufficiently mixed by a mixer.Afterward, the mixture was fed to a twin-screw extruder equipped with a20-mm vent sealed with nitrogen, and kneading and reaction were thencarried out under such conditions that the mixture was allowed to resideat 230° C. for 20 minutes, followed by pelletizing.

The resulting pellets were dissolved in hot xylol, and the solution wasthen filtered through a membrane filter (pore diameter=1.0 μm). To thefiltrate, methyl cellosolve was poured, and the deposited precipitatewas collected by filtration, sufficiently washed with methyl cellosolve,and then dried under reduced pressure to obtain a white solid. As aresult of the analysis of this solid, it was apparent that the solid wasan EP-modified polyethylene resin having a phenyl skeleton. The resultsof the elemental analysis and infrared absorption spectrum analysis ofthis solid were as follows.

    ______________________________________                                        Elemental analysis                                                                   C            H       N                                                 ______________________________________                                        Found:   79.8%          12.6%   6.7%                                          ______________________________________                                    

Infrared absorption spectrum analysis

Phenyl ring-based absorption 1600, 1502 cm⁻¹

EXAMPLE 26

Preparation of EP-modified polypropylene resin:

100 parts by weight of the pellets of a modified polypropylene resinobtained by the procedure of Example 1 and 20 parts by weight of thepellets of an epoxidized polyphenyleneether resin obtained by theprocedure of Reference Example 4 were sufficiently mixed by a mixer.Afterward, the mixture was fed to a twin-screw extruder equipped with a20-mm vent sealed with nitrogen, and kneading and reaction were thencarried out under such conditions that the mixture was allowed to resideat 280° C. for 10 minutes, followed by pelletizing.

The resulting pellets were dissolved in hot xylol, and the solution wasthen filtered through a membrane filter (pore diameter=1.0 μm). To thefiltrate, chloroform was poured, and the deposited precipitate wascollected by filtration, sufficiently washed with chloroform, and thendried under reduced pressure to obtain a solid. Next, this solid wasdissolved in hot xylol again, and methyl cellosolve was poured thereto.The deposited precipitate was collected by filtration, followed by thesame treatment as described above, to obtain a solid. As a result of theanalysis of this solid, it was apparent that the solid was anEP-modified polypropylene resin having a polyphenyleneether resinskeleton. The results of the elemental analysis of this solid were asfollows.

    ______________________________________                                        Elemental analysis                                                                   C            H       N                                                 ______________________________________                                        Found:   82.8%          13.0%   2.8%                                          ______________________________________                                    

EXAMPLE 27

A polypropylene resin composition consisting of 99 parts by weight of amodified polypropylene resin obtained by the procedure of Example 2, 0.6part by weight of dilauryl thiodipropionate and 0.4 part by weight ofpentaerythrityl-tetrakis 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate!was kneaded at 210° C. for 6 minutes by a mixing roll, and then kneadedand pelletized by an extruder. The resulting pellets were molded by aninjection molding machine to prepare test pieces for flammabilitydetermination having a thickness of 1/16 inch.

By the use of these test pieces, a test was conducted in accordance withthe vertical flammability testing method specified under Subject 94 ofUnderwriters Laboratories Inc., U.S.A. As a result, the flammability ofthese test pieces was found to be Level V-1. No melt dripped duringcombustion and each burnt test piece retained its original shape well.The above-mentioned polypropylene resin composition therefore hadexcellent flame retardancy.

EXAMPLE 28

In accordance with the same procedure as in Example 27, test pieces wereprepared from a polypropylene resin composition consisting of 80 partsby weight of the pellets of a modified polypropylene resin obtained bythe procedure of Example 1, 19 parts by weight of ammonium polyphosphate(trade name Exolit 422, made by Hoechst A. G.), 0.6 part by weight ofdilauryl thiodipropionate and 0.4 part by weight ofpentaerythrityl-tetrakis 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate!.

For these test pieces, a flammability test was conducted by the sameprocedure as in Example 27. As a result, the flammability of these testpieces was found to be Level V-0 and each burnt test piece retained itsoriginal shape well. In addition, it was understood that thesimultaneous use of the modified polypropylene resin regarding thepresent invention and phosphoruses could exert a synergistic effect,whereby the flammability could be further improved. The above-mentionedpolypropylene resin composition therefore had excellent flameretardancy.

EXAMPLES 29 TO 32

A polyethylene resin composition consisting of 85 parts by weight of thepellets of a modified polyethylene resin obtained by the procedure ofExample 4 and 15 parts by weight of each phosphoruses shown in Table 2was kneaded at 180° C. for 6 minutes by a mixing roll, and the thuskneaded material was then pelletized by an extruder. In accordance withthe same procedure as in Example 27, test pieces for flammabilitydetermination were prepared from the obtained pellets, and a test wasthen conducted. The results are shown in Table 2.

As shown in Table 2, it was understood that the simultaneous use of themodified polyethylene resin regarding the present invention and thephosphoruses could further improve the flammability and was excellent inflame retardancy.

                  TABLE 2                                                         ______________________________________                                                        Flame Retardancy                                                      Kind of       Level of UL                                                                             Melt                                          Example Phosphoruses  Standard 94                                                                             Dripping                                      ______________________________________                                        29      2-ethylhexyldiphenyl                                                                         V-0      None                                                  phosphate                                                             30      Tris(tridecyl)-                                                                              V-1      None                                                  phosphite                                                             31      Diethyl N,N-bis(2-                                                                           V-1      None                                                  hydroxyethyl)amino-                                                           methylphosphonate                                                     32      Ethylenebistris(2-                                                                           V-1      None                                                  cyanoethyl)phosphin                                                           oxide                                                                 ______________________________________                                    

EXAMPLE 33

The pellets of a modified polyamide resin obtained by the procedure ofExample 8 were molded by an injection molding machine to prepare testpieces for flammability determination having a thickness of 1/16 inch.

For these test pieces, a flammability test was conducted by the sameprocedure as in Example 27. As a result, the flammability of these testpieces was found to be level V-1 and their char formability wasexcellent, and each burnt test piece retained its original shape well.In consequence, it was apparent that the above-mentioned modifiedpolyamide resin had excellent flame retardancy.

EXAMPLE 34

A polyamide resin composition consisting of 96 parts by weight of thepellets of a modified polyamide resin obtained by the procedure ofExample 8 and 4 parts by weight of isocyanuric acid was sufficientlymixed by a mixer, and the mixture was then kneaded and pelletized by anextruder in which a cylinder temperature was set to 260° C. The thusformed pellets were molded by an injection molding machine to preparetest pieces for flammability determination having a thickness of 1/16inch.

For these test pieces, a flammability test was conducted by the sameprocedure as in Example 27. As a result, the flammability of these testpieces was found to be Level V-0 and each burnt test piece retained itsoriginal shape well. In addition, it was understood that thesimultaneous use of the modified polyamide resin regarding the presentinvention and an isocyanuric acid could exert a synergistic effect,whereby the flammability could be further improved. The above-mentionedpolyamide resin composition therefore had excellent flame retardancy.

EXAMPLE 35

A polyester resin composition consisting of 93 parts by weight of thepellets of a modified polyester resin obtained by the procedure ofExample 7 and 7 parts by weight of tris(2-hydroxyethyl)isocyanurate wassufficiently mixed by a mixer, and the mixture was then kneaded andpelletized by an extruder in which a cylinder temperature was set to280° C. The thus formed pellets were molded by an injection moldingmachine to prepare test pieces for flammability determination having athickness of 1/16 inch.

For these test pieces, a flammability test was conducted by the sameprocedure as in Example 27. As a result, the flammability of these testpieces was found to be Level V-0 and each burnt test piece retained itsoriginal shape well. In addition, it was understood that thesimultaneous use of the modified polyester resin regarding the presentinvention and an isocyanuric acid could exert a synergistic effect,whereby the flammability could be further improved. The above-mentionedpolyester resin composition therefore had excellent flame retardancy.

EXAMPLE 36

30 parts by weight of an EP-modified PP wax obtained by the procedure ofExample 24 and 5 parts by weight of cyanuric acid were first mixed by ahot roll. Next, 40 parts by weight of an epoxy resin (trade name Epicoat#828, made by Yuka Shell Epoxy Co., Ltd.) and 25 parts by weight ofmethylhexahydrophthalic anhydride were added thereto, and they were thenmixed by the hot roll to obtain an epoxy resin composition. Afterward,this composition was poured into a casting plate and then cured toprepare test pieces for flammability determination having a thickness of1/16 inch.

For these test pieces, a flammability test was conducted by the sameprocedure as in Example 27. As a result, the flammability of these testpieces was found to be Level V-0 and each burnt test piece retained itsoriginal shape well.

As shown in Examples 34 to 36, it could been understood that theflame-retarding method of the resins regarding the present inventioncould provide the excellent flame retardancy in various kinds of resinssuch as thermoplastic resins and thermosetting resins, and thesimultaneous employment of the each modified resin and/or theEP-modified resin regarding the present invention and each of anisocyanuric acid or a cyanuric acid could exert a synergistic effect,whereby the flammability could be further improved.

EXAMPLE 37

A polyphenyleneether resin composition consisting of 45 parts by weightof a modified polyphenyleneether resin obtained by the procedure ofExample 5, 30 parts by weight of a modified polystyrene resin obtainedby the procedure of Example 6, 10 parts by weight of isocyanuric acidand 15 parts by weight of ammonium polyphosphate (trade name Exolit 422,made by Hoechst A. G.) was mixed by a Henschel mixer, and the mixturewas then kneaded and pelletized by an extruder. Next, the thus formedpellets were molded by an injection molding machine to prepare testpieces for flammability determination having a thickness of 1/16 inch.

For these test pieces, a flammability test was conducted by the sameprocedure as in Example 27. As a result, the flammability of these testpieces was found to be Level V-0 and each burnt test piece retained itsoriginal shape well. The above-mentioned polyphenyleneether resincomposition therefore had excellent flame retardancy.

EXAMPLE 38

Kneading and reaction were carried out by the same procedure as inExample 5 except that 10 parts by weight of norbornenecarboguanamine inExample 5 was replaced with 20 parts by weight of the same, followed bypelletizing, to obtain a modified polyphenyleneether resin. Furthermore,kneading and reaction were carried out by the same procedure as inExample 6 except that 5 parts by weight of norbornenecarboguanamine inExample 6 was replaced with 15 parts by weight of the same. Next, thereaction product was pelletized to obtain a modified polystyrene resin.

A polystyrene resin composition comprising 20 parts by weight of thismodified polyphenyleneether resin, 67 parts by weight of this modifiedpolystyrene resin, 9 parts by weight of triphenyl phosphate and 4 partsby weight of ammonium sulfate was sufficiently mixed by a mixer, and themixture was then kneaded and pelletized by an extruder in which acylinder temperature was set to 250° C. The thus formed pellets weremolded by an injection molding machine to prepare test pieces forflammability determination having a thickness of 1/16 inch.

For these test pieces, a flammability test was conducted by the sameprocedure as in Example 27. As a result, the flammability of these testpieces was found to be Level V-0 and each burnt test piece retained itsoriginal shape well. The above-mentioned polystyrene resin compositiontherefore had excellent flame retardancy.

EXAMPLES 39 TO 47

A polypropylene resin composition comprising 78 parts by weight of amodified polypropylene resin obtained by the procedure of Example 1, 18parts by weight of ammonium polyphosphate (trade name Exolit 422, madeby Hoechst A. G.), 3 parts by weight of an amino group-containingcompound shown in Table 3, 0.6 part by weight of dilaurylthiodipropionate and 0.4 part by weight of pentaerythrityl-tetrakis3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate! was treated and tested inthe same procedure as in Example 27. The results are shown in Table 3.

As shown in Table 3, it could be understood that according to theflame-retarding method of the resins regarding the present invention,compositions comprising the modified resins regarding the presentinvention were extremely excellent in self-extinguishing properties, andthe burnt test pieces of the compositions could retain their originalshape well. Furthermore, the simultaneous employment of each modifiedresin, at least one of phosphorusus and at least one of aminogroup-containing compounds could exert the synergistic effect, wherebythe flammability could be further improved.

                  TABLE 3                                                         ______________________________________                                                          Flame Retardancy                                                    Amino group-    Level of UL                                                                             Melt                                        Example containing compound                                                                           Standard 94                                                                             Dripping                                    ______________________________________                                        39      N,N-bis(2-amino-                                                                              V-0       None                                                ethyl)piperazine                                                      40      N-(2-aminoethyly                                                                              V-0       None                                                morpholine                                                            41      N-(2-aminoethyl)                                                                              V-0       None                                                piperidine                                                            42      Dicyandiamide   V-0       None                                        43      Guanidine phosphate                                                                           V-0       None                                        44      Reaction product of                                                                           V-0       None                                                ethylenediamine-                                                              formaldehyde                                                                  (1/2 molar ratio)                                                     45      Reaction product                                                                              V-0       None                                                of piperazine-                                                                formaldehyde                                                                  (1/2 molar ratio)                                                     46      Pentamethylenehexamine                                                                        V-0       None                                        47      Pentaethylenehexamine                                                                         V-0       None                                        ______________________________________                                    

EXAMPLE 48

Thermal stability test of modified polyphenyleneether resin:

For a modified polyphenyleneether resin obtained by the procedure ofExample 5, thermogravimetric analysis (TG) was made at a temperaturerise of 10° C./min in an air atmosphere. As a result, the temperature ata mass reduction ratio of 5 wt % was 434° C.

On the other hand, for a raw material polyphenyleneether resin used inExample 5, the thermogravimetric analysis was made under the sameconditions as described above, and as a result, the temperature at amass reduction ratio of 5 wt % was 401° C.

EXAMPLE 49

Thermal stability test of modified polystyrene resin:

For a modified polystyrene resin obtained by the procedure of Example 6,thermogravimetric: analysis was made under the same conditions as inExample 48. As a result, the temperature at a mass reduction ratio of 5wt % was 334° C.

On the other hand, for a raw material polystyrene resin used in Example6, the thermogravimetric analysis was made under the same conditions asdescribed above, and as a result, the temperature at a mass reductionratio of 5 wt % was 299° C.

EXAMPLE 50

Thermal stability test of modified polymethacrylic resin:

For a modified polymethacrylic resin obtained by the procedure ofExample 9, thermogravimetric analysis was made under the same conditionsas in Example 48. As a result, the temperature at a mass reduction ratioof 5 wt % was 303° C.

On the other hand, for a raw material polymethacrylic resin used inExample 9, the thermogravimetric analysis was made under the sameconditions as described above, and as a result, the temperature at amass reduction ratio of 5 wt % was 285° C.

EXAMPLE 51

Thermal stability test of modified polypropylene resin:

For a modified polypropylene resin obtained by the procedure of Example1, thermogravimetric analysis was made under the same conditions as inExample 48. As a result, the temperature at a mass reduction ratio of 5wt % was 283° C.

On the other hand, for a raw material polypropylene resin used inExample 1, the thermogravimetric analysis was made under the sameconditions as described above, and as a result, the temperature at amass reduction ratio of 5 wt % was 267° C.

EXAMPLE 52

Thermal stability test of modified polyethylene resin:

For a modified polyethylene resin obtained by the procedure of Example17, thermogravimetric analysis was made under the same conditions as inExample 48. As a result, the temperature at a mass reduction ratio of 5wt % was 385° C.

On the other hand, for a raw material polyethylene resin used in Example17, the thermogravimetric analysis was made under the same conditions asdescribed above, and as a result, the temperature at a mass reductionratio of 5 wt % was 297° C.

As described in Examples 48 to 52, in the modified resins regarding thepresent invention, the temperature at a mass reduction ratio of 5 wt %could be remarkably heightened, and therefore the thermal stability ofthe resins could remarkably be improved as compared with the unmodifiedresin.

EXAMPLE 53

Thermal stability test of modified polyphenyleneether resin:

The pellets of a modified polyphenyleneether resin obtained by theprocedure of Example 5 were dissolved in chloroform, and the chloroformsolution was then filtered through a membrane filter (pore diameter=1.0μm) to obtain a chloroform-insoluble solid. Next, thischloroform-insoluble matter was poured into hot methyl cellosolve, andthe solution was similarly filtered to obtain an insoluble solid.Afterward, this insoluble solid was dried under reduced pressure, andthe weight of the dried solid was then measured. As a result, thecontent of the insoluble solid was 0.05 wt % based on the weight of themodified polyphenyleneether resin.

Furthermore, an unkneaded raw material polyphenyleneether resin used inExample 5 was treated in the same manner as described above, and as aresult, the content of the insoluble solid was 0.03 wt % based on theweight of the resin.

As described above, the insoluble solid content of the modifiedpolyphenyleneether resin regarding the present invention was very loweven after kneading and molding under heating at a high temperature andwas substantially equal to that of the raw material resin before thekneading. The above-mentioned polyphenyleneether resin therefore wasexcellent in thermal stability at the kneading and molding/working.

COMPARATIVE EXAMPLE 4

Thermal stability test of polyphenyleneether resin:

Kneading was carried out by the same procedure as in Example 5 exceptthat 10 parts by weight of norbornenecarboguanamine in Example 5 was notused, followed by pelletizing.

The pellets were treated in the same manner as in Example 53, and theweight of an insoluble solid was then measured. As a result, the contentof the insoluble solid was 4.61% by weight based on the weight of thekneaded resin.

As described above, in the unmodified polyphenyleneether resin, thecontent of the insoluble solid remarkably increased withmolding/working, and therefore the resin was poor in thermal stabilityand the molding/working and the like were noticeably limited

EXAMPLE 54

Thermal stability test of polyphenyleneether resin:

A polyphenyleneether resin composition comprising a polyphenyleneetherresin consisting of 42 parts by weight ofpoly-2,6-dimethyl-1,4-phenylene ether component in which an intrinsicviscosity η! was 0.58, 52 parts by weight of a modified polystyreneresin obtained by the procedure of Example 6 and 6 parts by weight of ahydrogenated SBS rubber component was mixed by a mixer, and molten,kneaded and then pelletized by a twin-screw extruder in which a cylindertemperature was set to 280° C. Next, the resulting pellets were moldedinto test pieces for Izod impact strength measurement having a thicknessof 1/8 inch by an injection molding machine in which a cylindertemperature was set to 280° C. These test pieces were allowed to standfor 200 hours in a hot air circulating thermostatic chamber set to 130°C. to make an aging test. The Izod impact strength was measured beforeand after the aging test in accordance with ASTM D256, and the resultsare shown in Table 4.

COMPARATIVE EXAMPLE 5

A treatment and a test were carried out by the same procedure as inExample 54 except that a modified polystyrene resin obtained by theprocedure of Example 6 which was used in Example 54 was replaced withthe same polystyrene resin as described above polystyrene resin beforemodification. The results are shown in Table 4.

                  TABLE 4                                                         ______________________________________                                                    Izod Impact Strength (Note 1)                                                 (1/8 inch notched)                                                            (kg/cm/cm)                                                                    Before Aging                                                                           After Aging                                              ______________________________________                                        Example 54    12.7       7.1 (56)                                             Comp. Ex. 5   12.6       5.2 (41)                                             ______________________________________                                         Note 1: Each value in the parenthesis means a retention ratio (%) of the      Izod impact strength after the aging to that before the aging.           

EXAMPLES 55 TO 56

Thermal stability test of polyphenyleneether resin:

A treatment and a test were carried out by the same procedure as inExample 54 except that the following additive was added to apolyphenyleneether resin composition of Example 54. The results areshown in Table 5.

                  TABLE 5                                                         ______________________________________                                                                 Izod Impact Strength                                        (1/8 inch notched)                                                            Additive          (kg/cm/cm)                                                          Amount    Before   After                                              Kind    (Note 1)  Aging    Aging                                       ______________________________________                                        Ex. 55   Triethylene-                                                                            0.2       12.8   9.2 (72)                                           tetramine                                                            Ex. 56   Tris(nonyl-                                                                             0.2       12.7   7.6 (60)                                           phenyl)                                                                       phosphite                                                            ______________________________________                                         Note 1: The amount was wt % based on the polyphenyleneether resin.       

EXAMPLE 57

Thermal stability test of polyethylene resin:

A polyethylene resin composition comprising 94 parts by weight of apolyethylene resin (trade name HIZEX 6200BP, made by MitsuiPetrochemical Industries, Ltd.), 1 part by weight of a fine copperpowder and 5 parts by weight of a modified polyethylene resin obtainedby the procedure of Example 4 was kneaded at 160° C. for 6 minutes by amixing roll, and then compression-molded at 150° C. under 200 kg/cm² for5 minutes to obtain a sheet film.

For this sheet film, an accelerated test of heat deterioration was madeunder an air atmosphere in a hot pack oven set to a temperature of 150°C. A point of time when the color of this test piece changed wasregarded as a deterioration starting point, and on the basis of a timeuntil this deterioration starting point, the thermal stability of theresin composition was judged. The results are shown in Table 6.

Furthermore, a treatment and a test were carried out by the sameprocedure as described above except that 5 parts by weight of themodified polyethylene obtained by the procedure of Example 4 was notadded to the above-mentioned polyethylene resin composition, and theresults are shown as "Comparative Example 6" in Table 6.

                  TABLE 6                                                         ______________________________________                                                   Period (days) till                                                            Start of Deterioration                                             ______________________________________                                        Example 57   20 days or more                                                  Comp. Ex. 6  1 day                                                            ______________________________________                                    

EXAMPLE 58

Thermal stability test of polypropylene resin:

A polypropylene resin composition comprising 94 parts by weight of apolypropylene resin (trade name MITSUI NOBLEN JS-G, made by MitsuiToatsu Chemicals, Inc.), 1 part by weight of a fine copper powder and 5parts by weight of a modified polypropylene resin obtained by theprocedure of Example 1 was kneaded at 210° C. for 6 minutes by a mixingroll, and then compression-molded at 190° C. under 200 kg/cm² for 5minutes to obtain a sheet film.

For this sheet film, a treatment and a test were carried out by the sameprocedure as in Example 57, and the results are shown in Table 7.

Furthermore, a treatment and a test were carried out by the sameprocedure as described above except that 5 parts by weight of themodified polypropylene resin obtained by the procedure of Example 1 wasnot added to the above-mentioned polypropylene resin composition, andthe results are shown as "Comparative Example 7" in Table 7.

                  TABLE 7                                                         ______________________________________                                                   Period (days) till                                                            Start of Deterioration                                             ______________________________________                                        Example 58   20 days or more                                                  Comp. Ex. 7  1 day                                                            ______________________________________                                    

EXAMPLE 59

Compatibilization test of binary resin composed of polyphenyleneetherresin and polyamideimide resin:

80 parts by weight of modified polyphenyleneether resin pellets obtainedby the procedure of Example 5 and 20 parts by weight of a polyamideimideresin (trade name TORON 4203T, made of Amoko Co., Ltd.) were mixed by aHenschel mixer, and the mixture was molten, kneaded and then pelletizedby a twin-screw extruder in which a cylinder temperature was set to 330°C.

The thus obtained binary resin composition was observed by an electronmicroscope, and as a result, a resin melt had a sea-and-island structurein which spheres having a controlled diameter of about 2.7 μm wereuniformly dispersed. Thus, the binary resin composition was excellent incompatibility.

EXAMPLE 60

Compatibilization test of binary resin composed of polyphenyleneetherresin and EP rubber:

70 parts by weight of modified polyphenyleneether resin pellets obtainedby the procedure of Example 5 and 30 parts by weight of a modified EPrubber obtained by the procedure of Example 10 were mixed by a Henschelmixer, and the mixture was molten, kneaded and then pelletized by atwin-screw extruder in which a cylinder temperature was set to 330° C.

The thus obtained binary resin composition was observed by an electronmicroscope, and as a result, a resin melt had a sea-and-island structurein which spheres having a controlled diameter of about 1.6 μm wereuniformly dispersed. Thus, the binary resin composition was excellent incompatibility.

EXAMPLE 61

Compatibilization test of tertiary resin composed of polyamide resin,polyphenyleneether resin and polystyrene resin:

A resin composition comprising 45 parts by weight of modifiedpolyphenyleneether resin pellets obtained by the procedure of Example 5,50 parts by weight of a polystyrene resin and 5 parts by weight of ahydrogenated SBS rubber was mixed by a Henschel mixer, and the mixturewas molten, kneaded and then pelletized by a twin-screw extruder inwhich a cylinder temperature was set to 300° C. After 50 parts by weightof the pellets was finely ground, 50 parts by weight of a modifiedpolyamide resin obtained by the procedure of Example 8 was added to thefinely ground pellets, and this resin composition was then mixed by theHenschel mixer. Next, the mixture was molten, kneaded and thenpelletized by a twin-screw extruder in which a cylinder temperature wasset to 280° C.

The thus obtained tertiary resin composition was observed by an electronmicroscope, and as a result, a resin melt had a sea-and-island structurein which spheres having a controlled diameter of about 1.6 μm wereuniformly dispersed. Thus, the tertiary resin composition was excellentin compatibility.

EXAMPLE 62

Compatibilization test of binary resin composed of polyphenyleneetherresin and polypropylene resin:

80 parts by weight of poly-2,6-dimethyl-1,4-phenyleneether in which anintrinsic viscosity η! was 0.42 and 20 parts by weight of an EP-modifiedpolypropylene resin obtained by the procedure of Example 26 were mixedby a mixer, and the mixture was molten, kneaded and then pelletized by atwin-screw extruder in which a cylinder temperature was set to 330° C.

The thus obtained binary resin composition was observed by an electronmicroscope, and as a result, a resin melt had a sea-and-island structurein which spheres having a controlled diameter of about 1.l μm wereuniformly dispersed. Thus, the binary resin composition was excellent incompatibility.

EXAMPLE 63

Compatibilization test of binary resin composed of saturated polyesterresin and polypropylene resin:

80 parts by weight of a saturated polyester resin (Teijin PBT ResinTRB-H, made by Teijin Limited) and 20 parts by weight of a modifiedpolypropylene resin obtained by the procedure of Example 2 were mixed bya Henschel mixer, and the mixture was molten, kneaded and thenpelletized by a twin-screw extruder in which a cylinder temperature wasset to 260° C.

The thus obtained binary resin composition was observed by an electronmicroscope, and as a result, a resin melt had a sea-and-island structurein which spheres having a controlled diameter of about 2.3 μm wereuniformly dispersed. Thus, the binary resin composition was excellent incompatibility.

EXAMPLE 64

Compatibilization test of binary resin composed of polyamide resin andpolypropylene resin:

70 parts by weight of a polyamide resin (Toyobo Nylon T-802, made byToyobo Co., Ltd.), 30 parts by weight of a polypropylene resin (tradename MITSUI NOBLEN JS-G, made by Mitsui Toatsu Chemicals, Inc.), 3 partsby weight of a reaction product of 5-norbornene-2-carbonyl chloride andhexamethylenediamine (molar ratio=2/1) and 0.1 part by weight ofdilauryl thiodipropionate were sufficiently mixed by a Henschel mixer,and the mixture was then fed to a twin-screw extruder equipped with a20-mm vent sealed with nitrogen. Afterward, kneading and reaction werecarried out under such conditions that the mixture was allowed to resideat 250° C. for 20 minutes, followed by pelletizing.

The thus obtained binary resin composition was observed by an electronmicroscope, and as a result, a resin melt had a sea-and-island structurein which spheres having a controlled diameter of about 0.6 μm wereuniformly dispersed. Thus, the binary resin composition was excellent incompatibility.

EXAMPLE 65

Compatibilization test of binary resin composed of polyphenyleneetherresin and polyamide resin:

80 parts by weight of poly-2,6-dimethyl-1,4-phenylene ether in which anintrinsic viscosity η! was 0.42, 20 parts by weight of a polyamide resin(Toyobo Nylon T-802, made by Toyobo Co., Ltd.) and 3 parts by weight ofa norbornenecarboguanamine-formaldehyde condensate obtained by theprocedure of Reference Example 2 were sufficiently mixed by a Henschelmixer, and the mixture was then fed to a twin-screw extruder equippedwith a 20-mm vent sealed with nitrogen. Afterward, kneading and reactionwere carried out under such conditions that the mixture was allowed toreside at 280° C. for 20 minutes, followed by pelletizing.

The thus obtained binary resin composition was observed by an electronmicroscope, and as a result, a resin melt had a sea-and-island structurein which spheres having a controlled diameter of about 0.5 μm wereuniformly dispersed. Thus, the binary resin composition was excellent incompatibility.

As described in Examples 59 to 65, it was understood that in thecompatibilization method of the resins regarding the present invention,the employment of the modified resins of the present invention couldremarkably improve the compatibilization between the different kinds ofresins.

EXAMPLE 66

Compatibilization test of binary resin composed of polyamide resin andpolypropylene resin:

70 parts by weight of a polyamide resin (Toyobo Nylon T-802, made byToyobo Co., Ltd.) and 30 parts by weight of EP-modified polypropyleneresin pellets obtained by the procedure of Example 22 were mixed by aHenschel mixer, and the mixture was molten, kneaded and then pelletizedby a twin-screw extruder in which a cylinder temperature was set to 220°C.

The thus obtained binary resin composition was observed by an electronmicroscope, and as a result, a resin melt had a sea-and-island structurein which spheres having a controlled diameter of about 1.1 μm wereuniformly dispersed. Thus, the binary resin composition was excellent incompatibility.

EXAMPLE 67

Compatibilization test of binary resin composed of polystyrene resin andpolyethylene resin:

80 parts by weight of a polystyrene resin (Topolex 570-02, made byMitsui Toatsu Chemicals, Inc.) and 20 parts by weight of EP-modifiedpolyethylene resin pellets obtained by the procedure of Example 25 weremixed by a Henschel mixer, and the mixture was molten, kneaded and thenpelletized by a twin-screw extruder in which a cylinder temperature wasset to 230° C.

The thus obtained binary resin composition was observed by an electronmicroscope, and as a result, a resin melt had a sea-and-island structurein which spheres having a controlled diameter of about 2.7 μm wereuniformly dispersed. Thus, the binary resin composition was excellent incompatibility.

As described in Examples 66 and 67, it was understood that in thecompatibilization method of the resins regarding the present invention,the employment of the EP modified resins of the present invention couldremarkably improve the compatibilization between the different kinds ofresins.

COMPARATIVE EXAMPLE 8

A treatment was carried out by the same procedure as in Example 66except that EP-modified polypropylene resin pellets obtained by theprocedure of Example 22 which was used in Example 66 were replaced witha polypropylene resin (trade name MITSUI NOBLEN JS-G, made by MitsuiToatsu Chemicals, Inc.), thereby obtaining pelletized resin composition.

The thus obtained resin composition was observed by an electronmicroscope, and as a result, a resin melt had a sea-and-islandstructure, but in this structure, there were spherical and ellipticalparticles having uncontrolled diameters in a wide range of from 5 to 100μm. Thus, this resin composition was extremely poor in compatibility.

EXAMPLE 68

Surface wettability test of modified polypropylene resin:

Polypropylene resin pellets obtained by the procedure of Example 1 weredissolved in hot xylol, and the solution was then filtered through amembrane filter (pore diameter=1.0 μm). To the filtrate, methylcellosolve was poured, and the deposited precipitate was collected byfiltration, sufficiently washed with methyl cellosolve, and then driedunder reduced pressure to obtain a white solid. Next, this solid waspress-molded at a temperature of 220° C. under a press pressure of 50kg/cm² for 5 minutes to obtain a molded plate having a thickness of 1mm.

A surface wettability test was carried out by the use of this moldedplate. That is to say, a wet index standard liquid for a wettabilitytest (made by WAKO Pure Chemical Industries) was applied in a belt formon the molded plate by a cotton swab. As a result, it was apparent thatwhen the standard liquid of 36 dyne/cm (23°±2° C.) was appliedthereonto, the original belt form of the liquid was maintained, and inother words, the surface kept wet, even after a certain time hadelapsed.

On the other hand, another molded plate was prepared under the samecondition as described above from raw material polypropylene resinpellets used in Example 1. By the use of this molded plate, a surfacewettability test was carried out in a manner similar to the above, andas a result, it was apparent that when a standard liquid of 32 dyne/cm(23°±2° C.) was applied thereonto, the liquid immediately became theform of a ball, and in other words, the surface did not wet at all.

As described above, the modified polypropylene resin regarding thepresent invention was much more excellent in surface wettability ascompared with the unmodified polypropylene resin.

COMPARATIVE EXAMPLE 9

Surface wettability test of polypropylene resin composition:

100 parts by weight of a polypropylene resin (trade name MITSUI NOBLENJS-G, made by Mitsui Toatsu Chemicals, Inc.), 10 parts by weight ofadipoguanamine and 0.1 part by weight of dilauryl thiodipropionate weresufficiently mixed by a Henschel mixer, and the mixture was then fed toa twin-screw extruder equipped with a 20-mm vent sealed with nitrogen.Afterward, kneading was carried out under such conditions that themixture was allowed to reside at 230° C. for 10 minutes, followed bypelletizing, to obtain a polypropylene resin composition.

Next, a molded plate was prepared from the pellets in a manner similarto Example 68, and by the use of this molded plate, a surfacewettability test was made. As a result, the molded plate did not wet,even when a standard liquid of 32 dyne/cm (23°±2° C.) was appliedthereonto. The surface wettability of the pellets was substantiallyequal to that of an unmodified polypropylene resin, and so the surfacewettability was not excellent.

EXAMPLE 69

Coating properties test of modified polypropylene resin composition:

48 parts by weight of a polypropylene resin (trade name MITSUI NOBLENBJ5H, made by Mitsui Toatsu Chemicals, Inc.), 22 parts by weight of amodified polypropylene resin obtained by the procedure of Example 1, 22parts by weight of an EP rubber (trade name JSR EP01P, made by JapanSynthetic Rubber Co., Ltd.), 8 parts by weight of a ground EPDM rubber(trade name JSR EP33, made by Japan Synthetic Rubber Co., Ltd.) and 0.05part by weight of Iruganox 1010 (trade name, made by Ciba-Geigy) weresufficiently mixed by a Henschel mixer, and the mixture was kneaded andthen pelletized by a twin-screw extruder in which a cylinder temperaturewas set to 210° C. The pellets were molded by an injection moldingmachine to prepare a test plate for coating having a thickness of 1/8inch. Next, the surface of this test plate was washed and then dried,and then coated with a two-part curing type polyurethane resincomprising 100 parts by weight of Orester Q186 (made by Mitsui ToatsuChemicals, Inc., nonvolatile content=50%) and 18 parts by weight ofOrester NP2000 (made by Mitsui Toatsu Chemicals, Inc., nonvolatilecontent=75%) so that film thickness might be 15 fm, and the polyurethaneresin was then cured at 80° C. for 50 minutes.

In the coating film on the coated test plate, cissing, blister and thelike were not observed, and in an adhesion test (a tape peeling test ona grid pattern), the coating film was not peeled at all, and thereforethe coating properties of the modified polypropylene resin compositionwere extremely good.

EXAMPLE 70

Coating properties test of modified polypropylene resin composition:

A test plate was prepared by the same procedure of Example 69 from 48parts by weight of a polypropylene resin (trade name MITSUI NOBLEN BJ5H,made by Mitsui Toatsu Chemicals, Inc.), 22 parts by weight of apolypropylene resin (trade name MITSUI NOBLEN JS-G, made by MitsuiToatsu Chemicals, Inc.), 22 parts by weight of a modified EP rubberobtained by the procedure of Example 10, 8 parts by weight of a groundEPDM rubber (trade name JSR EP33, made by Japan Synthetic Rubber Co.,Ltd.) and 0.05 part by weight of Iruganox 1010 (trade name, made byCiba-Geigy), and the test plate was coated.

In the coating film on the coated test plate, cissing, blister and thelike were not observed, and in an adhesion test (a tape peeling test ona grid pattern), the coating film was not peeled at all, and thereforethe coating properties of the modified polypropylene resin compositionwere extremely good.

COMPARATIVE EXAMPLE 10

Coating properties test of polypropylene resin composition:

A test plate was prepared by the same procedure as in Example 69 exceptthat 20 parts by weight of a modified polypropylene resin obtained bythe procedure of Example 1 which was used in Example 69 was replacedwith a polypropylene resin (trade name MITSUI NOBLEN JS-G, made byMitsui Toatsu Chemicals, Inc.), and this test plate was coated.

In an adhesion test (a tape peeling test on a grid pattern), the coatingfilm on the coated test plate was completely peeled, and therefore thecoating properties of the polypropylene resin composition were extremelypoor.

As described in Examples 69 and 70, the polypropylene resin compositionscomprising the modified resins regarding the present invention were muchmore excellent in coating properties as compared with the unmodifiedcomposition.

EXAMPLE 71

80 parts by weight of an EP-modified polypropylene resin pelletsobtained by the procedure of Example 22 and 20 parts by weight of anEP-modified EP rubber obtained by the procedure of Example 23 weresufficiently mixed by a mixer, and the mixture was kneaded and thenpelletized by a twin-screw extruder in which a cylinder temperature wasset to 240° C. The pellets were molded by an injection molding machineto prepare a test plate for coating having a thickness of 1/8 inch.

This test plate was coated with an urethane coating material (trade nameOrester M83-42CX, made by Mitsui Toatsu Chemicals, Inc.) so that filmthickness might be 24 μm, and the coating material was then cured at 80°C. for 5 hours.

In the coating film on the coated test plate, cissing, blister and thelike were not observed, and in an adhesion test (a tape peeling test ona grid pattern), the coating film was not peeled at all, and thereforethe coating properties of the test plate were extremely good.

EXAMPLE 72

80 parts by weight of modified polyethylene resin pellets obtained bythe procedure of Example 4 and 20 parts by weight of a modified EPrubber obtained by the procedure of Example 10 were sufficiently mixedby a mixer, and the mixture was kneaded and then pelletized by atwin-screw extruder in which a cylinder temperature was set to 250° C.The pellets were molded by an injection molding machine to prepare atest piece for tensile shear strength measurement having a thickness of1/8 inch.

Next, the test piece was caused to adhere to an iron metal test piece at100° C. for 24 hours by the use of an adhesive composition prepared bymixing 50 parts by weight of an epoxy resin (trade name Konishi BondQuick Mender, made by Konishi Co., Ltd.) and 50 parts by weight of acuring agent to prepare a specimen based upon JIS K 6850.

The tensile shear strength of this specimen was measured in accordancewith JIS K 6850, and as a result, it was 41 Kgf/cm². Thus, the testpiece was excellent in adhesive properties.

EXAMPLE 73

EP-modified polypropylene resin pellets obtained by the procedure ofExample 22 were molded by an injection molding machine in which acylinder temperature was set to 240° C. to prepare a test piece fortensile shear strength measurement having a thickness of 1/8 inch.

Next, from this test piece, a specimen was prepared by the sameprocedure as in Example 72, and the tensile shear strength was thenmeasured. As a result, it was 87 Kgf/cm², and therefore the specimen wasexcellent in adhesive properties.

On the other hand, another specimen was prepared by the same procedureas described above except that an original polypropylene resin which didnot undergo the above-mentioned modification/EP modification was used,and the tensile shear strength was then measured. As a result, it was 8Kgf/cm², and therefore the specimen was extremely poor in adhesiveproperties.

As shown in Examples 69 to 73, it was apparent that according to thesurface modification method of the resins regarding the presentinvention, surface properties such as coating properties and adhesiveproperties could be improved by the use of the modified/EP-modifiedresins of the present invention.

EXAMPLE 74

Surface modification test of polypropylene resin:

A molded plate of a modified polypropylene resin obtained by theprocedure of Example 68 was coated and reacted withphenyltrichlorosilane as a silane coupling agent at room temperature for1 hour under a nitrogen atmosphere. Next, the surface of this coatedmolded plate was washed with toluene, and then dried with hot air.

For this coated molded plate, X-ray emission spectrochemical analysis(ESCA) was carried out, and as a result, it was apparent that theSi_(2p) /C_(1S) spectrum of the surface of the molded plate wasremarkably large, which meant that the surface of the molded plate wasmodified.

EXAMPLE 75

Dyeability test of modified polypropylene resin:

Modified polypropylene resin pellets obtained by the procedure ofExample 1 were dissolved in hot xylol, and the solution was thenfiltered through a membrane filter (pore diameter=1.0 μm). To thefiltrate, methyl cellosolve was poured, and the deposited precipitatewas collected by filtration, sufficiently washed with methyl cellosolve,and then dried under reduced pressure to obtain a white solid. Next,this solid was spun at a resin temperature of 250° C. for a residencetime of 10 minutes at a winding rate of 500 m/min and then stretched toobtain the fiber of the resin.

Next, this fiber was immersed at 90° C. for 60 minutes in a bath ratioof 1:40 in a 5% solution of an acid dye (trade name Amiryl Blue E-PRL,made by Sumitomo Chemical Co., Ltd.) adjusted to pH 5 with 30% aceticacid, thereby dyeing the fiber. The thus dyed fiber was furthersubjected to a soaping treatment in 2 g/l solution of Emarl Powder 40(trade name, made by Kao, Ltd.) at 60° C. for 5 minutes in a bath ratioof 1:30, whereby a dyeability test was carried out.

The dyeability of this fiber obtained from the modified polypropyleneresin was judged by the naked eye, and as a result, it was apparent thatthe dyeability was remarkably improved.

COMPARATIVE EXAMPLE 11

Dyeability test of polypropylene resin:

The same procedure as in Example 75 was carried out except that amodified polypropylene resin obtained by the procedure of Example 1which was used in Example 75 was replaced with a raw materialpolypropylene resin (trade name MITSUI NOBLEN JS-G, made by MitsuiToatsu Chemicals, Inc.) used in Example 1, thereby obtaining the fiberof the resin, and the dyeability test of the fiber was then made.

The dyeability of this fiber obtained from the polypropylene resin wasjudged by the naked eye, and as a result, it was apparent that thedyeability was very poor.

EXAMPLE 76

80 parts by weight of an epoxy group-containing resin (trade nameAlmatex #7610, made by Mitsui Toatsu Chemicals, Inc.), 12 parts byweight of a modified PP wax obtained by the procedure of Example 11 and8 parts by weight of 1,4-bis(4,6-diamino-s-triazin-2-yl)cyclohexane werefed to a kneader in which a cylinder temperature was set to 110° C.,followed by kneading, to obtain a solid resin. This solid resin wascoarsely ground by a coarse grinder, and then finely ground by anatomizer. The resulting powder was sifted through a 150-mesh sieve, andthe passed powder was then used for a test as a powdery resincomposition for coating. Next, a steel plate chemically treated withzinc phosphate was electrostatically coated so that a film thicknessmight be about 50 μm, and then subjected to a heat treatment at 210° C.for 30 minutes.

The coating film on the coated steel plate subjected to the heattreatment was excellent in smoothness (judged by the naked eye), andeven when the surface of the coating film was rubbed 50 times with acloth containing n-butanol, the coating film was not peeled. Inaddition, in an adhesion test (a tape peeling test on a grid pattern),the coating film was not peeled, and therefore the resin composition wasexcellent in coating properties.

EXAMPLE 77

85 parts by wight of an epoxy resin (trade name Epoky 815, made byMitsui Toatsu Chemicals, Inc.) and 15 parts by weight of an EP-modifiedPP wax obtained by the procedure of Example 22 were sufficiently mixedby a mixer to prepare a resin composition for coating. Next, agalvanized sheet steel was coated with this composition, and then heatedat 160° C. for 20 minutes to cure the same.

The coating film on the coated steel plate was excellent in smoothness(judged by the naked eye), and even when the surface of the coating filmwas rubbed 50 times with a cloth containing n-butanol, the coating filmwas not peeled. In addition, in an adhesion test (a tape peeling test ona grid pattern), the coating film was not peeled, and therefore theresin composition was excellent in coating properties.

As described in Examples 76 and 77, it could be understood that by usingthe modified resin and the EP-modified resin of the present invention inthe resin compositions for coating of the present invention, coatingproperties such as coating film smoothness, adhesive properties and thelike could be improved.

EXAMPLE 78

30 parts by weight of a modified polypropylene resin pellets obtained bythe procedure of Example 3, 30 parts by weight of a modified EP rubberobtained by the procedure of Example 10 and 40 parts by weight of amodified PP wax obtained by the procedure of Example 11 weresufficiently mixed by a mixer, and the mixture was then fed to atwin-screw extruder in which a cylinder temperature was set to 200° C.,and then kneaded thereby to obtain a resin composition for an adhesive.

This resin composition was applied onto a test plate of a polypropyleneresin (trade name MITSUI NOBLEN JS-G, made by Mitsui Toatsu Chemicals,Inc.) having a thickness of 1/8 inch and a metallic test plate made ofaluminum by means of a spray gun for a hot melt set to 180° C., therebypreparing a specimen based on JIS K 6850.

The tensile shear strength of this specimen was measured in accordancewith JIS K 6850, and as a result, it was 48 Kgf/cm². Thus, the resincomposition for an adhesive was excellent in adhesive properties.

EXAMPLE 79

80 parts by weight of an epoxy resin (trade name Epicoat #828, made byYuka Shell Epoxy Co., Ltd.) and 20 parts by weight of an EP-modified PPwax obtained by the procedure of Example 24 were sufficiently mixed by amixer, and 30 parts by weight of 4,4'-diaminodiphenylmethane was furtheradded thereto, followed by mixing, to prepare a resin composition for anadhesive.

A test plate of a polypropylene resin (trade name MITSUI NOBLEN JS-G,made by Mitsui Toatsu Chemicals, Inc.) having a thickness of 1/8 inchwas caused to adhere to a metallic test plate made of iron via thisresin composition at 120° C. for 6 hours, thereby preparing a specimenbased on JIS K 6850.

The tensile shear strength of this specimen was measured in accordancewith JIS K 6850, and as a result, it was 96 Kgf/cm². Thus, the resincomposition for an adhesive was excellent in adhesive properties.

As described in Examples 78 and 79, it could be understood that by usingthe modified resin and the EP-modified resin of the present invention inthe resin compositions for adhesives of the present invention, theadhesive properties between different kinds of materials could beremarkably improved.

What is claimed is:
 1. A method for preparing an epoxy-modified resinwhich comprises the step of reacting at least one selected from thegroup consisting of epoxides with one of the following:(i) a modifiedresin prepared by a process comprising the step of reacting, at atemperature range of from 200° to 450° C., a resin with a compoundrepresented by the formula (2) ##STR7## wherein R₁, R₂, R₃, R₄, R₅, R₆,R₇, R₈, and R₉ each is a hydrogen atom, an alkyl group having 1 to 4carbon atoms or a phenyl group, and they may be the same or different;and R₁₀, R₁₁, R₁₂ and R₁₃ each is a hydrogen atom or a group having oneor more carbon atoms, and they may be the same or different; (ii) amodified resin prepared by a process comprising the step of reacting, ata temperature range of from 200° to 450° C., a resin with a condensatehaving an average addition condensation degree of more than 1 which isobtained by subjecting (a) a compound represented by the formula (2)above, with the proviso that at least one of R₁₀, R₁₁, R₁₂ and R₁₃ is ahydrogen atom, (b) a co-condensable compound as an optional reactant and(c) an aldehyde to an addition condensation reaction; or (iii) amodified resin prepared by a process comprising the step of reacting, ata temperature range of from 200° to 450° C., a resin with an etherifiedcondensate having an average addition condensation degree of more than 1which is obtained by subjecting (a) a compound represented by theformula (2) above, with the proviso that at least one of R₁₀, R₁₁, R₁₂and R₁₃ is a hydrogen atom, (b) a co-condensable compound as an optionalreactant and (c) an aldehyde to an addition reaction or an additioncondensation reaction, and then subjecting the reaction product and atleast one alcohol selected from alcohols having 1-20 carbon atoms toetherification and optionally to simultaneous condensation.
 2. Themethod according to claim 1, wherein the reaction is carried out at atemperature range of from 150° to 400° C.
 3. The method according claim1, wherein the reaction is carried out by reactive processing.